JPH11255900A - Polyimidesiloxane used as indispensable component of adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyimidesiloxane which enables lamination of various metal foils and a heat-resistant supporting material at a relatively low temp., by employing a tetracarboxylic acid component and a diamine component composed of a diaminopolysiloxane and an arom. diamine. SOLUTION: This polyimidesiloxane has a logarithmic viscosity of 0.05-7 (at 0.5 g/100 ml in a solvent: N-methyl-2-pyrolidone and at 30 deg.C), an imidization rate of >=90% as measured by the infrared absorption spectrum analyzing method, and a softening point of 5-250 deg.C and an elastic modulus of 250 kg/mm<2> or less, of a film formed by the cast method from an org. solvent soln. Sixty mol.% or more of the tetracarboxylic acid component is composed of 2,3,3',4'- biphenyltetracarboxylic aid dianhydride residue and the remaining part, another org. tetracarboxylic acid component residue. Ten to 80 mol.% of the diamine component is composed of a diaminopolysiloxane residue and the residual group, another org. diamine residue.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an essential component of a heat-resistant adhesive which is soluble in an organic polar solvent obtained from a tetracarboxylic acid component and a diamine component comprising diaminopolysiloxane and aromatic diamine, has a low elastic modulus, and has a low elastic modulus. It relates to the polyimide siloxane used.

[0002] The polyimidesiloxane of the present invention comprises a heat-resistant adhesive used as one component of a heat-resistant adhesive, and a metal foil such as a copper foil and a heat-resistant supporting material (heat-resistant film,
(Inorganic sheet, etc.) can be performed at a relatively low temperature, and the laminate bonded with the heat-resistant adhesive has sufficient adhesive strength and excellent heat resistance. , Flexible wiring board, TAB (Ta
If used for the production of copper-clad substrates for pe Automated Bonding, etc., each substrate obtained using the heat-resistant adhesive
Various subsequent high-temperature processing steps such as soldering can be performed with confidence, and the quality of the final product can be increased, and the defect rate can be reduced.

[0003]

2. Description of the Related Art Conventionally, flexible wiring boards have been manufactured by bonding an aromatic polyimide film and a copper foil using an adhesive such as an epoxy resin or a urethane resin. However, when the flexible wiring board manufactured using a known adhesive is exposed to a high temperature in a subsequent soldering process, there is a problem that the adhesive layer causes blistering or peeling, and the heat resistance of the adhesive is high. There was a desire for improvement.

As the above-mentioned heat-resistant adhesive, an imide resin-based adhesive has been proposed. For example, N, N '-(4,
4'-diphenylmethane) bismaleimide and 4,4 '
Precondensates consisting of diaminodiphenylmethane are known. However, the precondensate itself is not suitable as an adhesive for a flexible circuit board because of its brittleness.

As a method for improving the above-mentioned disadvantage, an adhesive film (dry film) is formed from a resin composition obtained by mixing an aromatic polyimide obtained from benzophenonetetracarboxylic acid and an aromatic diamine and polybismaleimide, A method 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 pressure-bonded (see JP-A-62-232475 and JP-A-62-235382). .

However, the above-mentioned adhesive film has a softening point of 18 due to a high softening temperature of the aromatic polyimide.
0 ° C. or higher, and it is necessary to bond the polyimide film and the copper foil at a high temperature of about 260-280 ° C. and under a high pressure of about 30-60 kg / cm 2. In this case, it is extremely difficult to continuously laminate the polyimide film and the copper foil using a pressure roll made of an organic resin, which is a problem in terms of practicality.

[0007] As a coating composition for electronic parts such as wiring boards, a resin solution (varnish) obtained by blending an epoxy resin with an aromatic polyimide is used to form a wiring with a heat-resistant coating layer made of the resin cured product. Various proposals have been made to improve the adhesion to a plate or the like. However, known aromatic polyimide-based compositions, as described above, in the production of copper-clad substrate as "adhesive for bonding the copper foil and the aromatic polyimide film", the bonding or curing temperature is high Or, low compatibility between the aromatic polyimide and the epoxy resin or the compatibility between the aromatic polyimide and the solvent,
Alternatively, there is a problem that the adhesive layer after bonding and curing is not flexible, and thus cannot be actually used as an adhesive.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the known adhesives by applying an adhesive solution, drying, laminating a copper foil, and forming an adhesive layer. Through a process consisting of drying (curing), it can be used in organic polar solvents suitable for "heat-resistant adhesives that exhibit high adhesiveness at high temperatures", which enables the heat-resistant film and various metal foils to be bonded together. It is an object to provide a soluble polyimide siloxane.

[0009]

That is, the present invention provides:
Logarithmic viscosity (measured concentration: 0.5 g / 100 ml solvent, solvent: N-methyl-2-pyrrolidone, measurement temperature: 30 ° C.) used as an essential component of the heat-resistant adhesive
Is 0.05-7, the imidation ratio measured by infrared absorption spectroscopy is 90% or more, the softening temperature measured on a film formed from the organic solvent solution by a casting method is 5-250 ° C, A polyimide siloxane having a rate of 250 kg / mm 2 or less.

In the above-mentioned polyimide siloxane, each component is preferably such that at least 60 mol% of the tetracarboxylic acid component is a 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride residue and the balance is 3%. , 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4
4'-diphenylethertetracarboxylic dianhydride,
Bis (3,4-dicarboxyphenyl) methane, 2,2
-Bis (3,4-dicarboxyphenyl) propane or pyromellitic dianhydride is an aromatic tetracarboxylic acid component residue, 10 to 80 mol% of a diamine component is a diaminopolysiloxane residue, and the remainder is 1,4-diaminodiphenyl ether, 1,3-diaminodiphenyl ether, 1,3-di (4-aminophenoxy) benzene, 1,4-di (4-aminophenoxy) benzene,
2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, Bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4
-(4-aminophenoxy) phenyl] hexafluoropropane or 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane which is an aromatic diamine residue (diaminopolysiloxane residue and aromatic (In a total amount of 100 mol% with a diamine residue).

The polyimide siloxane of the present invention has a logarithmic viscosity (measured concentration: 0.5 g / 100 ml solvent,
Solvent: N-methyl-2-pyrrolidone, measured concentration: 30
C) is 0.05-7, preferably 0.1-3, especially 0.1.
It is preferably a polymer having a concentration of about 45-3 and further capable of being uniformly dissolved in any of organic polar solvents (particularly amide solvents) at a concentration of at least 3% by weight, particularly about 5 to 40% by weight. . The polyimide siloxane of the present invention has an imidation ratio of 90% or more, particularly 95% or more, as measured by an infrared absorption spectrum analysis method, or an absorption peak relating to an amide-acid bond of a polymer in the infrared absorption spectrum analysis. It is preferable that the imidation ratio is so high that substantially no absorption is found and only absorption peaks related to imide ring bonds are observed. In particular, the imidization rate is 10
It is preferably 0%.

Further, the polyimide siloxane of the present invention has an elastic modulus of 250 k when formed into a film.
g / mm2 or less, especially about 0.1-200 kg / mm2,
More preferably, the softening temperature (secondary transition temperature) is about 0.5 to 150 ° C.
Thermal decomposition initiation temperature is preferably 250 ° C. or higher, particularly 300 ° C.
That is all.

The method for producing the polyimidesiloxane of the present invention is as follows: 2,3,3 ', 4'-biphenyltetracarboxylic acid (tetracarboxylic acid, tetracarboxylic dianhydride or tetracarboxylic acid ester) is added to about 60 mol%.
An aromatic tetracarboxylic acid component containing
2NR-[-Si (R1) (R2) -O-] n- (R3)
(R4) -R-NH2 (where R represents a divalent hydrocarbon residue, R1, R2, R3, and R4 represent a lower alkyl group or a phenyl group, and n is 3-60, preferably 5-50 Diaminopolysiloxane 20)
A phenol-based solvent, an amide-based solvent, a compound-based solvent having a sulfur atom, and a glycol, using a diamine component composed of -80 mol% and the aromatic diamine 20-80 mol% (total 100 mol%). At high temperature (particularly preferably 1
(At a temperature of 40 ° C. or higher), a polymerization method in which both monomer components are polymerized and imidized.

In the present invention, 2,3,3 ', 4'
-Biphenyltetracarboxylic dianhydride (a-BPD
A) is optimal in terms of solubility of the polyimidesiloxane obtained by polymerization with the diamine component in an organic polar solvent and compatibility with an epoxy compound.

Further, as a method for producing the polyimidesiloxane of the present invention, 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 have a logarithmic viscosity of 0.1. A method may be used in which a polyamic acid having a molecular weight of at least 05 is produced, and the polyamic acid is imidized by a known method to produce a soluble polyimide siloxane.

Further, as a process for producing the polyimidesiloxane of the present invention, an imidosiloxane oligomer obtained by polymerizing an excess amount of the above-mentioned aromatic tetracarboxylic acid component and a diamine component consisting of only diaminopolysiloxane is used.
(X component: the average degree of polymerization is about 1-10, and has an acid or an acid anhydride group at the terminal.) And the excess amount of the diamine component consisting of only the aromatic tetracarboxylic acid component and the aromatic diamine. Imide oligomer obtained by polymerizing
(Y component: degree of polymerization is about 1-10, and has an amino group at a terminal).
A method for producing a block polyimide siloxane by mixing and reacting the components so that the ratio of the total acid component to the total diamine component thereof is approximately equimolar can be also suitably mentioned.

In the polyimide siloxane of the present invention, if the polyimide siloxane is produced mainly from tetracarboxylic acids other than biphenyltetracarboxylic acids, it becomes hardly soluble in an organic polar solvent or a heat-resistant adhesive is used. Even if it is mixed with an epoxy resin in order to obtain it, the compatibility is deteriorated, so that it is not suitable.

As the aromatic diamine component in the present invention, 1,4-diaminodiphenyl ether, 1,3-
Diaminodiphenyl ether, 1,3-di (4-aminophenoxy) benzene, 1,4-di (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3
-Aminophenoxy) phenyl] propane, bis [4-
(4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone,
2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane or 2,2-bis [4-
(3-Aminophenoxy) phenyl] hexafluoropropane, particularly preferably 2,2-bis [4- (4-aminophenoxy) phenyl] propane, is used.

Examples of the organic polar solvent include N, N-dimethylacetamide (DMAC), N, N-diethylacetamide, N, N-dimethylformamide, N, N-
Amide-based solvents such as diethylformamide and N-methyl-2-pyrrolidone (NMP); solvents containing a sulfur atom such as dimethylsulfoxide, diethylsulfoxide, dimethylsulfone, diethylsulfone and hexamethylsulfonamide; cresol, phenol Phenol solvents such as phenol, xylenol, acetone, methanol,
Solvents having an oxygen atom in the molecule, such as ethanol, ethylene glycol, dioxane, and tetrahydrofuran, and other solvents such as pyridine and tetramethylurea can be mentioned. If necessary, benzene, toluene, xylene It is also possible to use other types of organic solvents such as aromatic hydrocarbon solvents such as solvent naphtha and benzonitrile in combination.

The polyimide siloxane of the present invention is used as one component of a heat-resistant adhesive. The heat-resistant adhesive is 10 to 500 parts by weight of a bismaleimide-triazine resin, a bismaleimide resin or an organic compound having a cyanate group, and 0 to 55 parts by weight of an epoxy compound having an epoxy group, based on 100 parts by weight of polyimide siloxane. Those containing 5 parts by weight, especially 5 to 40 parts by weight as a resin component are preferred.

The bismaleimide-triazine resin, which is another component of the heat-resistant adhesive, is, for example, an imide group obtained from a bismaleimide component and a triazine monomer or prepolymer component having a cyanate group. And a known thermosetting resin composition having a triazine ring, which may be modified with acrylates, divinylbenzene, styrene, triallyl isocyanate or the like in an amount of 0 to 30% by weight. "B" manufactured by Mitsubishi Gas Chemical Co., Ltd.
Preferable examples include "T resin".

The bismaleimide resin includes, for example, maleic anhydride and a diamine compound [diaminobenzene, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diaminodiphenyl- Ter, 4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, etc.] and an unsaturated (double bond) group based on maleic acid obtained at both ends. Preferably, "Bismaleimide" manufactured by Mitsui Toatsu Chemical Co., Ltd., "ATU-BMI resin" manufactured by Ajinomoto Co., Ltd., "Kelimide" manufactured by Nippon Polyimide Co., Ltd., "Technohemie" Compimide "and the like.

Examples of the organic compound having a cyanate group include bisphenol A dicyanate, bis (4-cyanatephenyl) ether, and 1,1,1-tris (4-cyanate). Triphenyl) ethane and the like, and particularly “XU-71787” manufactured by The Dow Chemical Company.
−02 ”and the like.

The above-mentioned bismaleimide-triazine resin,
Examples of the epoxy compound having an epoxy group used in a heat-resistant adhesive together with a bismaleimide resin or an organic compound having a cyanate group include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and phenol-type epoxy resin.
Examples include "epoxy compounds having one or more epoxy groups" such as a lunovolak type epoxy resin, a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, and a glycidylamine type epoxy resin. They can be used together. The epoxy resin has a melting point of 90 ° C. or less, especially 0-
Those having a temperature of about 80 ° C or liquid at a temperature of 30 ° C or lower are particularly preferred.

In particular, in the above-mentioned heat-resistant adhesive, the soluble polyimide siloxane of the present invention has an elastic modulus of 150 or less.
100 parts by weight of a polyimide siloxane having a softening temperature of 5 ° C. or more (especially 5-250 ° C.), a bismaleimide-triazine resin, a bismaleimide resin, At least one selected from the group consisting of cyanate compound resins
10-500 parts by weight of thermosetting resin (particularly 12-15
0 parts by weight) and a heat-resistant adhesive containing 0-50 parts by weight (5-40 parts by weight) of an epoxy compound having an epoxy group as a resin component is, for example, a metal foil such as a copper foil and a fragrance. When a copper-clad board is formed by bonding a heat-resistant film such as an aromatic polyimide film with this heat-resistant adhesive, and further forming a wiring board by etching the copper foil and the like of the copper-clad board, The wiring board has a radius of curvature of 80
mm, which is optimal because it does not show a large warp.

In the above-mentioned heat-resistant adhesive, a curing agent and a curing accelerator of an epoxy compound (resin) may be used in combination. However, in some cases, the combination of a curing agent and the like is not preferable. The heat-resistant adhesive contains, as a main component, a resin component having the above composition ratio of the polyimide siloxane of the present invention, a thermosetting resin, and an epoxy compound (particularly preferably 90% by weight).
As described above, it is more preferable that the total amount of the resin components is 3 to 50% by weight, more preferably 5 to 4% by weight in a suitable organic polar solvent.
It may be a solution composition of a heat-resistant adhesive which is uniformly dissolved at a concentration of 0% by weight.

The solution composition of the above-mentioned heat-resistant adhesive has a solution viscosity (30 ° C.) of 0.1 to 1000 poise, particularly 0.2 to 5000 poise, and more preferably 1 to 100 poise.
It is preferably about 0 poise, and if necessary, an inorganic filler such as silicon dioxide (for example, “Aerosil 200” of Nippon Aerosil Co., Ltd.) may be added to the solution composition.

The above-mentioned heat-resistant adhesive has a softening point (temperature at which softening starts on a hot plate) of a composition comprising only an uncured resin component of 150 ° C. or less, particularly 120 ° C. or less, and more preferably 100 ° C. or less. It is preferable that the temperature is not higher than ° C. The above-mentioned heat-resistant adhesive is preferably used at 150 to 400 ° C., more preferably 1 to 400 ° C.
It is preferable that the material can be thermally cured by heating to a curing temperature of 80 to 350 ° C (particularly 200 to 300 ° C). The heat-resistant adhesive may contain a small proportion of other thermosetting resin such as phenol resin as a resin component.

The above-mentioned heat-resistant adhesive is prepared by applying a solution composition in which all of the above-mentioned resin components are uniformly dissolved in an organic polar solvent to a heat-resistant film surface such as an appropriate metal foil or an aromatic polyimide film, or The solvent was removed to 1% by weight or less by coating on a film surface made of a thermoplastic resin such as polyester or polyethylene and drying the applied layer at a temperature of 80 to 200 ° C. for 20 seconds to 100 minutes. (Preferably the residual ratio of the solvent is particularly 0.5% by weight or less.) A thin film of the heat-resistant adhesive in an uncured state (having a thickness of 1-2
A dry film or sheet having a thickness of 00 μm can be formed.

The uncured heat-resistant adhesive thin film produced as described above has suitable flexibility, and is wound around a paper tube or the like, or subjected to a punching process such as a punching method. Further, for example, a laminated sheet in which a thin layer of an uncured heat-resistant adhesive is formed on the above-mentioned heat-resistant or thermoplastic film may be formed on a metal foil or heat-resistant film for transfer destination. It is also possible to transfer it to

In order to form a laminate such as a copper-clad substrate by bonding a heat-resistant film and a metal foil using the above-mentioned heat-resistant adhesive, for example, a thin-film heat-resistant film formed as described above is used. Through the adhesive layer, the heat-resistant film and the metal foil at a temperature of 80-200 ° C, especially 140-180 ° C,
The laminate is laminated under pressure, and the laminate is heated at a temperature of about 200 to 300 ° C. for 1 to 30 hours to heat and cure the heat resistant adhesive layer. By doing so, the above-mentioned laminate can be easily and continuously manufactured without any trouble.

The above-mentioned heat-resistant adhesive is bonded to a heat-resistant film such as an aromatic polyimide film, a polyamide film, a polyetheretherketone, a PEEK film, a polyethersulfone film and an appropriate metal foil such as a copper foil. It can be suitably used for

In this specification, the logarithmic viscosity (ηin
h) means that an aromatic polyimide or imide oligomer is uniformly dissolved in N-methyl-2-pyrrolidone to prepare a resin solution so that the resin component concentration becomes 0.5 g / 100 ml solvent, and the solution is prepared. And the solvent viscosity of only the solvent were measured at 30 ° C., and the values were determined by the following formula. Logarithmic viscosity (ηinh) = [ln (solution viscosity / solvent viscosity)] / concentration of solution The softening temperature of the polyimide siloxane film is determined by measuring the relationship between the temperature and the elastic modulus of the polymer, and determining the viscoelastic peak. (Higher temperature side) (corresponding to the second order transition temperature). Furthermore, the elastic modulus is
It is obtained from the elastic modulus at room temperature when the relationship between the temperature and the elastic modulus of the polymer is measured.

[0034]

The present invention will be described below in further detail with reference to examples. In each of the following examples, the siloxane unit content in the polymer indicates the ratio (mol%) of the amount of diaminosiloxane used to the total amount of diamino compounds used. The workability of the adhesive layer at 30 ° C. was evaluated in terms of tackiness (tackability with a protective film), punching property, and workability during heat bonding. ：: good, 普通: normal, ×: poor The adhesive strength was measured by performing a T-type peel test on the laminate at a peel speed of 50 mm / min using a tensile tester manufactured by Intesco Corporation. Furthermore, the "radius of curvature" of a wiring board formed by etching a copper-clad substrate in which a copper foil and a polyimide film are bonded using an adhesive is formed.
Was determined by the following formula in JIS C-6418. Curvature radius (mm) = L2 / 8h (where L represents the length of the sample and h represents its height)

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

The mixture was stirred at 50 ° C. for 2 hours in a stream of nitrogen to produce an amic acid oligomer, and then the reaction mixture was heated to about 200 ° C., and stirred at that temperature for 3 hours to form an anhydride group at the terminal. (A-1 component, average degree of polymerization: 1) having the following formula:

REFERENCE EXAMPLE 2 The amounts of the respective components were calculated as follows: (a) 0.042 mol of 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (a-BPDA), (b) ω, ω'- Bis (3-aminopropyl) polydimethylsiloxane (X-22, manufactured by Shin-Etsu Silicon Co., Ltd.)
-161AS, n: 9) 0.036 mol, and (c) N
In the same manner as in Reference Example 1 except that 175 g of -methyl-2-pyrrolidone (NMP) was used, an imidosiloxane oligomer having a terminal anhydride group (A-2, average degree of polymerization: 5) was produced.

[Production of Imido Oligomer] Reference Example 3 (a) was placed in a glass flask having a capacity of 500 ml.
0.044 mol of 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (a-BPDA), (b) 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) 0.066 mol and (c) 160 g of N-methyl-2-pyrrolidone (NMP) were charged,

In a nitrogen stream, the mixture was stirred at 50 ° C. for 2 hours to form an amic acid oligomer. Then, the reaction solution was heated to about 200 ° C., and stirred at that temperature for 3 hours to give amino groups at the terminals. (B-1 component, average degree of polymerization: 1) having the following formula:

REFERENCE EXAMPLE 4-5 The amount of each component was calculated as follows: (a) 0.054 mol of 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (a-BPDA) (Reference Example 4) or 0 0.055 mol (Reference Example 5),
(b) 0.063 mol (Reference Example 4) or 0.060 mol (Reference Example 5) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), and (c)
Imide oligomer B-2 having an amino group at the terminal (average degree of polymerization: 5) and B-3 in the same manner as in Reference Example 3 except that 165 g of N-methyl-2-pyrrolidone (NMP) was used.
(Average degree of polymerization: 10).

[Production of Polyimide Siloxane] Example 1 (Reference Example 6) 14.14 g (0.01 g) of an imidosiloxane oligomer having an acid anhydride group at the terminal (component A-1) produced in Reference Example 1
055 mol) of a 20% by weight NMP solution and Reference Example 4
Imide oligomer having an amino group at the terminal prepared in
(Component B-2) 24.33 g (0.0055 mol) of 2
A 0 wt% NMP solution was charged into a glass flask having a capacity of 500 ml and stirred at 50 ° C for 1 hour in a nitrogen stream to form a block polymer.
C., and stirred at that temperature for 3 hours to produce a polyimidesiloxane (block). The obtained polyimide siloxane had an imidation ratio of 100%, a logarithmic viscosity of 0.49, and a siloxane unit content of 2%.
2.22 mol%. The elastic modulus and softening temperature of a polyimidesiloxane film (thickness: about 50 μm) formed from the polyimidesiloxane reaction solution by a casting method were measured. Elastic modulus: 125 kg / mm2 Softening temperature: 235 ° C

Example 2 (Reference Example 7) 0.0055 mol of the imidosiloxane oligomer having a terminal acid anhydride group (component A-2) prepared in Reference Example 2 was 0.0055 mol.
0% by weight NMP solution and the imide oligomer having a terminal amino group prepared in Reference Example 5 (component B-2)
A polyimide siloxane (block) having an imidation ratio of substantially 100% was produced in the same manner as in Example 1 (Reference Example 6) except that a 0025 mol 20% by weight NMP solution was used. The obtained polyimide siloxane has an imidization ratio of 100% and a logarithmic viscosity of 0.1.
45, and the content of siloxane units was 33.33 mol%. A polyimide siloxane film (thickness: about 50 μm) formed from this polyimide siloxane
For m), its elastic modulus and softening temperature were measured. Elastic modulus: 32 kg / mm2 Softening temperature: 157 ° C

Example 3 (Reference Example 8) 0.01 mol of an imidosiloxane oligomer having a terminal acid anhydride group (component A-1) prepared in Reference Example 1 in a 20% by weight NMP solution, and Reference Example 3 Imide oligomer having terminal amino group (component B-1) 0.01
Example 1 except that a molar 20 wt% NMP solution was used.
(Reference Example) In the same manner as in 6, the imidization ratio was substantially 10
Polyimide siloxanes (blocks) of 0% were produced. The obtained polyimide siloxane had an imidization ratio of 100%, an intrinsic viscosity of 0.48, and a siloxane unit content of 40.00 mol%. The elastic modulus and softening temperature of the polyimide siloxane film (thickness: about 50 μm) formed from the polyimide siloxane were measured. Elastic modulus: 58 kg / mm2 Softening temperature: 186 ° C

Example 4 (Reference Example 9) 0.0033 mol of an imidosiloxane oligomer having a terminal acid anhydride group (component A-2) prepared in Reference Example 2
0% by weight NMP solution and the imide oligomer having a terminal amino group prepared in Reference Example 4 (component B-2)
A polyimide siloxane (block) having an imidation ratio of substantially 100% was produced in the same manner as in Example 1 (Reference Example 6) except that a 0033 mol 20% by weight NMP solution was used. The obtained polyimide siloxane has an imidization ratio of 100% and a logarithmic viscosity of 0.1.
And the siloxane unit content was 46.20 mol%. A polyimide siloxane film (thickness: about 50 μm) formed from this polyimide siloxane
For m), its elastic modulus and softening temperature were measured. Elastic modulus: 23 kg / mm2 Softening temperature: 112 ° C

Example 5 (Reference Example 10) 0.01 mol of an imidosiloxane oligomer having a terminal acid anhydride group (component A-2) prepared in Reference Example 2 in a 20% by weight NMP solution, and Reference Example 3 Imide oligomer having terminal amino group (component B-1) 0.01
Example 1 except that a molar 20 wt% NMP solution was used.
(Reference Example) In the same manner as in 6, the imidization ratio was substantially 10
Polyimide siloxanes (blocks) of 0% were produced. The obtained polyimide siloxane had an imidization ratio of 100%, an intrinsic viscosity of 0.49, and a siloxane unit content of 66.67 mol%. The elastic modulus and softening temperature of the polyimide siloxane film (thickness: about 50 μm) formed from the polyimide siloxane were measured. Elastic modulus: 1 kg / mm2 Softening temperature: 12 ° C

Example 6 (Reference Example 11) 0.03 mol of a 20% by weight NMP solution of an imidosiloxane oligomer having a terminal acid anhydride group (component A-1) prepared in Reference Example 1, and Reference Example 4 Imido oligomer having a terminal amino group (component B-2) 0.03
Example 1 except that a molar 20 wt% NMP solution was used.
(Reference Example) In the same manner as in 6, the imidization ratio was substantially 10
Polyimide siloxanes (blocks) of 0% were produced. The obtained polyimide siloxane had an imidization ratio of 100%, an intrinsic viscosity of 0.52, and a siloxane unit content of 22.22 mol%. The elastic modulus and softening temperature of the polyimide siloxane film (thickness: about 50 μm) formed from the polyimide siloxane were measured. Elastic modulus: 120 kg / mm2 Softening temperature: 234 ° C

Example 7 (Reference Example 12) In a glass flask having a capacity of 500 ml, (a) a
-BPDA: 0.054 mol, (b) diaminopolysiloxane (X-22-161A manufactured by Shin-Etsu Silicon Co., Ltd.)
S, n: 9) 0.012 mol, (c) BAPP: 0.04
After charging 2 mol and (d) NMP: 175 g,

In a nitrogen stream, the mixture was stirred at 50 ° C. for 2 hours to form an amic acid oligomer, and then the reaction solution was heated to about 200 ° C. and stirred at that temperature for 3 hours to obtain polyimide siloxane (random). Body, logarithmic viscosity: 0.59, siloxane unit content: 22.2 mol%, imidization ratio:
100%). With respect to a polyimide siloxane film (thickness: about 50 μm) formed by a casting method from the obtained polyimide siloxane reaction solution, its elastic modulus and softening temperature were measured. Elastic modulus: 130 kg / mm2 Softening temperature: 205 ° C

Example 8 (Reference Example 13) In a glass flask having a capacity of 500 ml, (a) a
-BPDA: 0.048 mol, (b) diaminopolysiloxane (X-22-161A manufactured by Shin-Etsu Silicon Co., Ltd.)
S, n: 9) 0.016 mol, (c) BAPP: 0.03
After charging 2 mol and (d) NMP: 165 g,

The mixture was stirred at 50 ° C. for 2 hours in a nitrogen stream to produce an amic acid oligomer, and then the reaction solution was heated to about 200 ° C. and stirred at that temperature for 3 hours to obtain polyimide siloxane (random). Body, logarithmic viscosity: 0.56, siloxane unit content: 33.3 mol%, imidization ratio:
100%). With respect to a polyimide siloxane film (thickness: about 50 μm) formed by a casting method from the obtained polyimide siloxane reaction solution, its elastic modulus and softening temperature were measured. Elastic modulus: 75 kg / mm2 Softening temperature: 200 ° C

Example 9 (Reference Example 14) In a glass flask having a capacity of 500 ml, (a) a
-BPDA: 0.054 mol, (b) diaminopolysiloxane (X-22-161A manufactured by Shin-Etsu Silicon Co., Ltd.)
S, n: 9) 0.018 mol, (c) BAPP: 0.03
After charging 6 mol and (d) NMP: 175 g,

In a nitrogen stream, the mixture was stirred at 50 ° C. for 2 hours to produce an amic acid oligomer, and then the reaction solution was heated to about 200 ° C. and stirred at that temperature for 3 hours to obtain polyimide siloxane (random). Body, logarithmic viscosity: 0.54, siloxane unit content: 33.33 mol%, imidation ratio: 100%). A polyimidesiloxane film (thickness: about 50 μm) formed by a casting method from the obtained polyimidesiloxane reaction solution,
The elastic modulus and softening temperature were measured. Elastic modulus: 71 kg / mm2 Softening temperature: 197 ° C

[Evaluation Test 1] (Example 1) Preparation of heat-resistant adhesive-1 Polyimide siloxane (block) prepared in Example 1 (Reference Example 6) was placed in a glass flask having a capacity of 500 ml. 25 g, bismaleimide-triazine resin (BT resin 3309T, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 65 g, epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd.)
Product name: Epicoat 152) 10 g, dioxane 200
g and stirred at room temperature (25 ° C.) for about 2 hours to prepare a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 0.5 poise). This solution composition maintained a uniform solution state (viscosity) even when left at room temperature for one week.

Production of Laminate Using Heat-Resistant Adhesive and Measurement of Adhesive Strength-1 A solution composition of this heat-resistant adhesive was applied to a polyimide film (Ube Industries, Ltd., trade name: UPILEX-S, thickness: 75 μm). A doctor blade is applied on top to a thickness of 125 μm, and the applied layer is then applied at 50 ° C. for 30 minutes.
The resultant was dried by heating at 100 ° C. for 30 minutes and at 170 ° C. for 20 minutes to form a heat-resistant adhesive layer (uncured dried layer, softening point: 25 ° C.) having a thickness of about 20 μm on the polyimide film. The workability of this adhesive layer at 30 ° C. is ○ (good)
Met.

The polyimide film having the heat-resistant adhesive layer and a copper foil (35 μm) were superposed and the laminate was heated at 160 ° C.
The laminate was pressed by passing it through a heated laminator roll while applying pressure.
1 hour at 180 ° C., 1 hour at 180 ° C., 1 hour at 200 ° C., 2
Heat treatment was performed at 20 ° C. for 5 hours and further at 250 ° C. for 6 hours in a nitrogen stream to cure the heat-resistant adhesive layer, thereby producing a laminate. About the obtained laminated body, adhesive strength (25
° C, 180 ° C). Adhesive strength (25 ° C): 0.9 kg / cm Adhesive strength (180 ° C): 1.3 kg / cm

[Evaluation Test 2] (Example 2) The types and amounts of the respective components were changed to 35 g of the polyimidesiloxane prepared in Example 1 (Reference Example 6) and 55 g of a bismaleimide-triazine resin (BT resin 3309T). And a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 1.6 poise) in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 10 g of epoxy resin (Epicoat 152). ), A heat-resistant adhesive layer (uncured dried layer, softening point: 35 ° C., workability at 30 ° C. is good), a laminate was manufactured, and the adhesive strength (25 ° C., 180 ° C.) was measured. . Adhesive strength (25 ° C): 1.1kg / cm Adhesive strength (180 ° C): 1.2kg / cm

[Evaluation Test 3] (Example 3) The type and amount of each component were determined by using 15 g of the polyimidesiloxane produced in Example 1 (Reference Example 6) and 75 g of a bismaleimide-triazine resin (BT resin 3309T). And a uniform composition of a heat-resistant adhesive solution (viscosity at 25 ° C: 0.3 poise) in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 8 g of epoxy resin (Epicoat 152). ), A heat-resistant adhesive layer (uncured dried layer, softening point: workability at 20 ° C., 30 ° C. is good), and a laminate was manufactured, and the adhesive strength (25 ° C., 180 ° C.) was measured. . Adhesive strength (25 ° C): 0.7 kg / cm Adhesive strength (180 ° C): 1.0 kg / cm

[Evaluation Test 4] (Example 4) The type and amount of each component were changed to 35 g of the polyimide siloxane produced in Example 1 (Reference Example 6) and 55 g of a bismaleimide-triazine resin (BT resin 3309T). And a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 2.5 poise) in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 5 g of epoxy resin (Epicoat 152). ), A heat-resistant adhesive layer (uncured dried layer, softening point: 35 ° C., workability at 30 ° C. is good), a laminate was manufactured, and the adhesive strength (25 ° C., 180 ° C.) was measured. . Adhesive strength (25 ° C): 1.2 kg / cm Adhesive strength (180 ° C): 1.3 kg / cm

[Evaluation Test 5] (Example 5) The types and amounts of the respective components were changed to 35 g of the polyimidesiloxane produced in Example 1 (Reference Example 6) and 55 g of a bismaleimide-triazine resin (BT resin 3309T). , And an epoxy resin (Epicoat 871, manufactured by Yuka Shell Epoxy Co., Ltd.), except that the composition was changed to 30 g in the same manner as in Evaluation Test-1 (Example 1). C .: 0.6 poise), heat-resistant adhesive layer (uncured dried layer, softening point: workability at 20.degree. C. and 30.degree. C. is good), laminate, and adhesive strength (25 ° C, 1
80 ° C.). Adhesive strength (25 ° C): 0.5 kg / cm Adhesive strength (180 ° C): 1.0 kg / cm

[Evaluation Test 6] (Example 6) The type and amount of each component were changed to 35 g of the polyimidesiloxane prepared in Example 2 (Reference Example 7) and 55 g of a bismaleimide-triazine resin (BT resin 3309T). And a uniform composition of a heat-resistant adhesive solution (viscosity at 25 ° C .: 0.2 poise) in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 10 g, and epoxy resin (Epicoat 871) was changed to 10 g. ), A heat-resistant adhesive layer (uncured dried layer, softening point: 35 ° C., workability at 30 ° C. is good), a laminate was manufactured, and the adhesive strength (25 ° C., 180 ° C.) was measured. . Adhesive strength (25 ° C): 0.7 kg / cm Adhesive strength (180 ° C): 1.2 kg / cm

[Evaluation Test 7] (Example 7) The type and amount of each component were changed to 35 g of the polyimidesiloxane produced in Example 3 (Reference Example 8) and 55 g of a bismaleimide-triazine resin (BT resin 3309T). And a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 0.3 poise) in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 10 g of epoxy resin (Epicoat 152). ), A heat-resistant adhesive layer (uncured dried layer, softening point: 35 ° C., workability at 30 ° C. is good), a laminate was manufactured, and the adhesive strength (25 ° C., 180 ° C.) was measured. . Adhesive strength (25 ° C): 0.8 kg / cm Adhesive strength (180 ° C): 0.7 kg / cm

[Evaluation Test 8] (Example 8) The type and amount of each component were changed to 35 g of the polyimidesiloxane produced in Example 4 (Reference Example 9) and 55 g of a bismaleimide-triazine resin (BT resin 3309T). And a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 0.3 poise) in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 10 g of epoxy resin (Epicoat 152). ), A heat-resistant adhesive layer (uncured dried layer, softening point: 35 ° C., workability at 30 ° C. is good), a laminate was manufactured, and the adhesive strength (25 ° C., 180 ° C.) was measured. . Adhesive strength (25 ° C): 0.5 kg / cm Adhesive strength (180 ° C): 0.5 kg / cm

[Evaluation Test 9] (Example 9) 35 g of the polyimidesiloxane prepared in Example 14 (Reference Example 6) and bismaleimide resin (bismaleimide, manufactured by Ajinomoto Co., Ltd.) Evaluation test except that 55 g of “bismaleimide ATU-BMI” and 10 g of epoxy resin (Epicoat 152) were used.
In the same manner as in Example 1 (Example 1), a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 0.6 poise), a heat-resistant adhesive layer (uncured dried layer, softening point: 70 ° C, 30 ° C
作業), the laminate is manufactured, and the adhesive strength (25
° C, 180 ° C). Adhesive strength (25 ° C): 0.9 kg / cm Adhesive strength (180 ° C): 1.3 kg / cm

[Evaluation Test 10] (Example 10) The type and amount of each component were determined by comparing 35 g of the polyimidesiloxane manufactured in Example 1 (Reference Example 6) with a cyanate compound [manufactured by The Dow Chemical Company]. "Cyanate compound XU-
71787-02 "], except that 55 g and 10 g of epoxy resin (Epicoat 152) were used.
In the same manner as in (Example 1), a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 1.2 poise), a heat-resistant adhesive layer (uncured dried layer, softening point: 25) ℃, the workability at 30 ° C is good), the laminate is manufactured, and the adhesive strength (25 ° C,
180 ° C.). Adhesive strength (25 ° C): 1.1kg / cm Adhesive strength (180 ° C): 1.2kg / cm

[Evaluation Test 11] (Example 11) 15 g of the polyimidesiloxane prepared in Example 1 (Reference Example 6), bismaleimide-triazine resin (BT resin 2160, Mitsubishi 55 g of an epoxy resin (Epicoat 1)
52) Evaluation test-1 except that the amount was changed to 10 g (Example 1)
In the same manner as described above, a solution composition of a uniform heat-resistant adhesive (25
Viscosity at 1.2 ° C.), a heat-resistant adhesive layer (uncured dried layer, softening point: workability at 35 ° C. and 30 ° C. is good), a laminate, and an adhesive strength (25 ℃, 180 ℃)
Was measured. Adhesive strength (25 ° C): 0.7 kg / cm Adhesive strength (180 ° C): 1.0 kg / cm

[Evaluation Test 12] (Example 12) The type and amount of each component were determined by comparing 15 g of the polyimidesiloxane produced in Example 1 (Reference Example 6), bismaleimide-triazine resin (BT resin 2160RX, Mitsubishi 35 g, manufactured by Gas Chemical Co., Ltd., and epoxy resin (Epico-
G) A uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 1.0 poise) and a heat-resistant adhesive layer in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 10 g. (Uncured dried layer, softening point: workability at 70 ° C., 30 ° C. is good), laminate is manufactured, and adhesive strength (25 ° C., 180
° C). Adhesive strength (25 ° C): 1.2 kg / cm Adhesive strength (180 ° C): 1.3 kg / cm

[Evaluation Test 13] (Example 13) 35 g of the polyimidesiloxane prepared in Example 1 (Reference Example 6), bismaleimide resin (bismaleimide, Mitsui Toatsu Chemicals, Inc.) 55)
g, and 10 g of epoxy resin (Epicoat 871), except that the test was conducted in the same manner as in Evaluation Test-1 (Example 1).
Solution composition of homogeneous heat resistant adhesive (viscosity at 25 ° C .: 0.1
6 poise), heat resistant adhesive layer (uncured dried layer,
Softening point: workability at 35 ° C. and 30 ° C.), a laminate was manufactured, and the adhesive strength (25 ° C., 180 ° C.) was measured. Adhesive strength (25 ° C): 0.5 kg / cm Adhesive strength (180 ° C): 1.0 kg / cm

[Evaluation Test 14] (Example 14) 55 g of the polyimidesiloxane prepared in Example 4 (Reference Example 9) and 35 g of a bismaleimide-triazine-based resin (BT resin 3309T) were determined based on the type and amount of each component. And a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 3.6 poise) in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 10 g of epoxy resin (Epicoat 152). ), A heat-resistant adhesive layer (uncured dried layer, softening point: 30 ° C., workability at 30 ° C. is good), a laminate was manufactured, and the adhesive strength (25 ° C., 180 ° C.) was measured. . Adhesive strength (25 ° C): 0.9kg / cm Adhesive strength (180 ° C): 0.8kg / cm

[Evaluation Test 15] (Example 15) The type and amount of each component were changed to 35 g of the polyimidesiloxane prepared in Example 4 (Reference Example 9) and 55 g of a bismaleimide-triazine resin (BT resin 3309T). , And epoxy resin (IPU-22 manufactured by Okamura Oil Co., Ltd.)
G) In the same manner as in Evaluation Test-1 (Example 1) except that the composition was changed to 10 g, a solution composition of a uniform heat-resistant adhesive (25 ° C.)
Viscosity: 1.1 poise), a heat-resistant adhesive layer (uncured dried layer, softening point: 30 ° C., workability at 30 ° C. is good), a laminate, and an adhesive strength (25 ° C.) , 180 ° C)
Was measured. Adhesive strength (25 ° C): 0.7 kg / cm Adhesive strength (180 ° C): 0.7 kg / cm

[Evaluation Test 16] (Example 16) 70 g of the polyimidesiloxane produced in Example 4 (Reference Example 9) and 10 g of a bismaleimide-triazine resin (BT resin 3309T) , And a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 15.6 poise) in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 20 g of epoxy resin (IPU-22G). , A heat-resistant adhesive layer (uncured dried layer, softening point: workability at 75 ° C. and 30 ° C. is Δ) and a laminate, and the adhesive strength (25 ° C., 180 ° C.) was measured. Adhesive strength (25 ° C): 0.9kg / cm Adhesive strength (180 ° C): 0.6kg / cm

[Evaluation Test 17] (Example 17) The types and amounts of the respective components were changed to 35 g of the polyimidesiloxane prepared in Example 1 (Reference Example 6) and 55 g of a bismaleimide-triazine resin (BT resin 3309T). And a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 2.2 poise) and heat-resistant adhesive in the same manner as in Evaluation Test-1 (Example 1) except that the amount of epoxy resin was changed to 0 g. Layer (uncured dried layer, softening point: 40 ° C., workability at 30 ° C. is good), laminate is manufactured, and adhesive strength (25 ° C., 180
° C). Adhesive strength (25 ° C): 1.2 kg / cm Adhesive strength (180 ° C): 1.4 kg / cm

[Evaluation Test 18] (Example 18) 35 g of the polyimidesiloxane prepared in Example 7 (Reference Example 12) and bismaleimide-
The same procedure as in Evaluation Test-1 (Example 1) was conducted, except that 55 g of a triazine-based resin (BT resin 3309T) and 10 g of an epoxy resin (Epicoat 152) were used. Viscosity at 25 ° C .: 0.6 poise), heat-resistant adhesive layer (uncured dried layer, softening point: 35 ° C., workability at 30 ° C. is good), laminate, and adhesive strength ( 25 ° C., 180 ° C.). Adhesive strength (25 ° C): 1.2 kg / cm Adhesive strength (180 ° C): 1.3 kg / cm

[Evaluation Test 19] (Example 19) 35 g of the polyimidesiloxane prepared in Example 8 (Reference Example 13) and bismaleimide-
The same procedure as in Evaluation Test-1 (Example 1) was conducted, except that 55 g of a triazine-based resin (BT resin 3309T) and 10 g of an epoxy resin (Epicoat 152) were used. Viscosity at 25 ° C .: 0.2 poise), heat-resistant adhesive layer (uncured dried layer, softening point: workability at 35 ° C. and 30 ° C. is good), laminate, and adhesive strength ( 25 ° C., 180 ° C.). Adhesive strength (25 ° C): 0.3 kg / cm Adhesive strength (180 ° C): 0.4 kg / cm

[Comparative Evaluation Test 1] (Comparative Example 1) The type and amount of each component were determined by using 20 g of the polyimide siloxane manufactured in Example 1 (Reference Example 6), 60 g of an epoxy resin (Epicoat 152), and curing. Agent: low-viscosity heat-resistant adhesive in the same manner as in Evaluation Test-1 (Example 1) except that 0.1 g of 2-phenylimidazole and 55 g of bismaleimide-triazine resin (BT resin 3309T) were used. And a heat-resistant adhesive layer (thickness: 25 μm) was formed. As a result of bending the polyimide film on which the adhesive layer was formed, many cracks occurred in the adhesive layer. Lamination of the polyimide film on which the heat resistant adhesive layer was formed and the copper foil was substantially impossible.

[Comparative Evaluation Test 2] (Comparative Example 2) 95 g of the polyimidesiloxane prepared in Example 2 (Reference Example 7), 5 g of the epoxy resin (Epicoat 152), and curing Agent: A solution composition of a low-viscosity heat-resistant adhesive, a heat-resistant adhesive layer (thickness) in the same manner as in Evaluation Test-1 (Example 1) except that 0.1 g of 2-phenylimidazole was used. : 25 μm). Lamination of the polyimide film on which the heat resistant adhesive layer was formed and the copper foil was substantially impossible.

[Evaluation Test 20] (Example 20) 55 g of the polyimidesiloxane prepared in Example 3 (Reference Example 8) and 35 g of a bismaleimide-triazine-based resin (BT resin 3309T) were determined based on the type and amount of each component. , And a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 25 poise) in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 10 g of epoxy resin (Epicoat 152). A heat resistant adhesive layer and a laminate are manufactured, and the adhesive strength (2
(5 ° C., 180 ° C.), and the warpage (curvature radius) after copper foil etching was measured. Adhesive strength (25 ° C): 1.95 kg / cm Adhesive strength (180 ° C): 0.90 kg / cm Radius of curvature: 110 mm

[Evaluation Test 21] (Example 21) 55 g of the polyimidesiloxane prepared in Example 2 (Reference Example 7) and 35 g of a bismaleimide-triazine-based resin (BT resin 3309T) were determined based on the type and amount of each component. , And a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 18 poises) in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 10 g of epoxy resin (Epicoat 152). A heat resistant adhesive layer and a laminate are manufactured, and the adhesive strength (2
(5 ° C., 180 ° C.), and the warpage (curvature radius) after copper foil etching was measured. Adhesive strength (25 ° C): 1.85 kg / cm Adhesive strength (180 ° C): 1.00 kg / cm Radius of curvature: 105 mm

[Evaluation Test 22] (Example 22) 55 g of the polyimidesiloxane prepared in Example 4 (Reference Example 9) and 35 g of a bismaleimide-triazine-based resin (BT resin 3309T) were measured for the type and amount of each component. , And a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 20 poises) in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 10 g of epoxy resin (Epicoat 152). A heat resistant adhesive layer and a laminate are manufactured, and the adhesive strength (2
(5 ° C., 180 ° C.), and the warpage (curvature radius) after copper foil etching was measured. Adhesive strength (25 ° C): 1.85 kg / cm Adhesive strength (180 ° C): 0.85 kg / cm Radius of curvature: 115 mm

[Evaluation Test 23] (Example 23) 55 g of the polyimidesiloxane prepared in Example 5 (Reference Example 10) and bismaleimide-
Except that 35 g of a triazine resin (BT resin 3309T) and 10 g of an epoxy resin (Epicoat 152) were used, a solution composition of a uniform heat-resistant adhesive was prepared in the same manner as in Evaluation Test-1 (Example 1). (Viscosity at 25 ° C .: 12 poise), heat-resistant adhesive layer and laminate were manufactured, and adhesive strength (2
(5 ° C., 180 ° C.), and the warpage (curvature radius) after copper foil etching was measured. Adhesive strength (25 ° C): 1.00 kg / cm Adhesive strength (180 ° C): 0.50 kg / cm Radius of curvature: ∞

[Evaluation Test 24] (Example 24) 55 g of the polyimidesiloxane prepared in Example 6 (Reference Example 11) and bismaleimide-
Except that 35 g of a triazine resin (BT resin 3309T) and 10 g of an epoxy resin (Epicoat 152) were used, a solution composition of a uniform heat-resistant adhesive was prepared in the same manner as in Evaluation Test-1 (Example 1). (Viscosity at 25 ° C .: 20 poise), heat-resistant adhesive layer and laminate were manufactured, and adhesive strength (2
(5 ° C., 180 ° C.), and the warpage (curvature radius) after copper foil etching was measured. Adhesive strength (25 ° C): 1.85 kg / cm Adhesive strength (180 ° C): 1.20 kg / cm Radius of curvature: 100 mm

[Evaluation Test 25] (Example 25) 35 g of the polyimidesiloxane produced in Example 4 (Reference Example 9) and 55 g of a bismaleimide-triazine-based resin (BT resin 3309T) were determined based on the type and amount of each component. , And a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 8 poise) in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 10 g of epoxy resin (Epicoat 152).
Manufacture a heat-resistant adhesive layer and a laminate, and bond strength (25 ° C,
180 ° C.), and the warpage (curvature radius) after copper foil etching was measured. Adhesive strength (25 ° C): 1.20 kg / cm Adhesive strength (180 ° C): 0.70 kg / cm Curvature radius: 105 mm

[Evaluation Test 26] (Example 26) The types and amounts of the respective components were changed to 35 g of the polyimidesiloxane produced in Example 4 (Reference Example 9) and 55 g of a bismaleimide-triazine resin (BT resin 3309T). , And a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 7 poise) and heat-resistant adhesive in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 10 g of epoxy resin (IPU22G). And a laminate, and the adhesive strength (25 ° C., 18
0 ° C.), and the warpage (curvature radius) after copper foil etching was measured. Adhesive strength (25 ° C): 1.50 kg / cm Adhesive strength (180 ° C): 0.80 kg / cm Radius of curvature: 120 mm

[Evaluation Test 27] (Example 27) 35 g of the polyimidesiloxane produced in Example 4 (Reference Example 9) and 55 g of a bismaleimide-triazine resin (BT resin 3309T) were measured for the type and amount of each component. , And a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 8 poise) in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 10 g of epoxy resin (Epicoat 871).
Manufacture a heat-resistant adhesive layer and a laminate, and bond strength (25 ° C,
180 ° C.), and the warpage (curvature radius) after copper foil etching was measured. Adhesive strength (25 ° C): 1.70 kg / cm Adhesive strength (180 ° C): 0.80 kg / cm Radius of curvature: 105 mm

[Evaluation Test 28] (Example 28) 55 g of the polyimidesiloxane produced in Example 4 (Reference Example 9) and 35 g of a bismaleimide-triazine resin (BT resin 3309T) were determined by changing the type and amount of each component. , And a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 20 poise) and heat-resistant adhesive in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 10 g of epoxy resin (IPU22G). And an adhesive layer (25 ° C., 1
80 ° C.) and the warpage (curvature radius) after copper foil etching was measured. Adhesive strength (25 ° C): 1.70 kg / cm Adhesive strength (180 ° C): 1.05 kg / cm Radius of curvature: 150 mm

[Evaluation Test 29] (Example 29) 55 g of the polyimidesiloxane prepared in Example 4 (Reference Example 9) and 35 g of a bismaleimide-triazine resin (BT resin 2160) were determined by changing the type and amount of each component. , And a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 15 poises) and heat-resistant adhesive in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 10 g of epoxy resin (IPU22G). And a laminate, and the adhesive strength (25 ° C., 18
0 ° C.), and the warpage (curvature radius) after copper foil etching was measured. Adhesive strength (25 ° C): 1.40 kg / cm Adhesive strength (180 ° C): 0.60 kg / cm Radius of curvature: 180 mm

[Evaluation Test 30] (Example 30) 55 g of the polyimidesiloxane prepared in Example 4 (Reference Example 9) and 35 g of a bismaleimide-triazine resin (BT resin 2160RX) were prepared. , And a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 16 poises) in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 10 g of epoxy resin (IPU22G).
Manufacture a heat-resistant adhesive layer and a laminate, and bond strength (25 ° C,
180 ° C.), and the warpage (curvature radius) after copper foil etching was measured. Adhesive strength (25 ° C): 1.30 kg / cm Adhesive strength (180 ° C): 0.55 kg / cm Curvature radius: 175 mm

[Evaluation Test 31] (Example 31) 55 g of the polyimidesiloxane prepared in Example 4 (Reference Example 9) and the cyanate compound 3
A uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 8 poises) and heat resistance were obtained in the same manner as in Evaluation Test-1 (Example 1) except that 5 g and 10 g of epoxy resin (IPU22G) were used. The adhesive layer and the laminate are manufactured, and the adhesive strength (2
(5 ° C., 180 ° C.), and the warpage (curvature radius) after copper foil etching was measured. Adhesive strength (25 ° C): 1.20 kg / cm Adhesive strength (180 ° C): 0.55 kg / cm Radius of curvature: 200 mm

[Evaluation Test 32] (Example 32) 70 g of the polyimidesiloxane prepared in Example 4 (Reference Example 9) and 10 g of a bismaleimide-triazine-based resin (BT resin 3309T) were determined in accordance with the type and amount of each component. , And a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 28 poise) and heat-resistant adhesive in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 20 g of epoxy resin (IPU22G). And an adhesive layer (25 ° C., 1
80 ° C.) and the warpage (curvature radius) after copper foil etching was measured. Adhesive strength (25 ° C): 1.65 kg / cm Adhesive strength (180 ° C): 0.55 kg / cm Radius of curvature: ∞

[Evaluation Test 33] (Example 33) 70 g of the polyimidesiloxane produced in Example 2 (Reference Example 7) and 10 g of a bismaleimide-triazine-based resin (BT resin 3309T) were determined by changing the type and amount of each component. , And a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 28 poise) and heat-resistant adhesive in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 20 g of epoxy resin (IPU22G). And an adhesive layer (25 ° C., 1
80 ° C.) and the warpage (curvature radius) after copper foil etching was measured. Adhesive strength (25 ° C): 1.90 kg / cm Adhesive strength (180 ° C): 0.70 kg / cm Radius of curvature: ∞

[Evaluation Test 34] (Example 34) 55 g of the polyimide siloxane, 35 g of a bismaleimide resin (bismaleimide), and an epoxy resin were prepared in the same manner as in Example 4 (Reference Example 9). (I
PU22G) A uniform heat-resistant adhesive solution composition (viscosity at 25 ° C: 15 poise), a heat-resistant adhesive layer, and a laminate in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 10 g. Was manufactured, and the adhesive strength (25 ° C., 180 ° C.) and the warpage (curvature radius) after copper foil etching were measured. Adhesive strength (25 ° C): 1.50 kg / cm Adhesive strength (180 ° C): 0.60 kg / cm Radius of curvature: ∞

[Evaluation Test 35] (Example 35) 55 g of the polyimide siloxane, 35 g of bismaleimide resin (bismaleimide), and the epoxy resin prepared in Example 4 (Reference Example 9) (I
PU22G) A uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 14 poise), a heat-resistant adhesive layer, and a laminate in the same manner as in Evaluation Test-1 (Example 1) except that the amount was changed to 10 g. Was manufactured, and the adhesive strength (25 ° C., 180 ° C.) and the warpage (curvature radius) after copper foil etching were measured. Adhesive strength (25 ° C): 1.65 kg / cm Adhesive strength (180 ° C): 0.80 kg / cm Radius of curvature: 105 mm

[Evaluation Test 36] (Example 36) 55 g of the polyimidesiloxane prepared in Example 9 (Reference Example 14) and bismaleimide-
35 g of a triazine-based resin (BT resin 3309T),
A uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 20 poises) was obtained in the same manner as in Evaluation Test-1 (Example 1) except that the amount of the epoxy resin and the epoxy resin (Epicoat 152) were changed to 10 g. The adhesive strength layer (2)
(5 ° C., 180 ° C.), and the warpage (curvature radius) after copper foil etching was measured. Adhesive strength (25 ° C): 1.80 kg / cm Adhesive strength (180 ° C): 1.00 kg / cm Radius of curvature: 105 mm

[0093]

Since the present invention is configured as described above, the following effects can be obtained.

The polyimide siloxane of the present invention has heat resistance, flexibility, and excellent solubility in an organic polar solvent, and the heat-resistant adhesive used as one component of the heat-resistant adhesive can be used for a copper foil or the like. Various metal foils and heat-resistant support materials (heat-resistant films, inorganic sheets, etc.) can be bonded at a relatively low temperature, and the laminate bonded with the heat-resistant adhesive has sufficient adhesive strength. And exhibit excellent heat resistance.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Tsutomu Funakoshi 3-10 Nakamiyakita-machi, Hirakata-shi, Osaka Ube Industries, Ltd. Inside Hirakata Laboratory Co., Ltd. (72) Inventor Tetsuji Hirano 3-10, Nakamiyakita-machi, Hirakata-shi, Osaka Ube Industries Hirakata Laboratory Co., Ltd.

Claims (4)

[Claims] A logarithmic viscosity (measurement concentration: 0.5 g / 100 ml solvent, solvent: N-methyl-2-pyrrolidone, measurement temperature: 30 ° C.) used as an essential component of the heat-resistant adhesive is 0.1. 05-7, the imidation ratio measured by infrared absorption spectroscopy is 90% or more, the softening temperature measured on a film formed from the organic solvent solution by a casting method is 5-250 ° C., and the elastic modulus is 250 kg.
/ Mm2 or less. 2. In each component, at least 60 mol% of the tetracarboxylic acid component is a 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride residue, and the remainder is 3,3', 4,4. '-Biphenyltetracarboxylic dianhydride, 3,3', 4
4'-benzophenonetetracarboxylic dianhydride, 3,
3 ', 4,4'-diphenylethertetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane or pyromellitic acid An aromatic tetracarboxylic acid component residue which is a dianhydride, and 10-8 of a diamine component
0 mol% is a diaminopolysiloxane residue, and the remainder is 1,
4-diaminodiphenyl ether, 1,3-diaminodiphenyl ether, 1,3-di (4-aminophenoxy) benzene, 1,4-di (4-aminophenoxy) benzene, 2,2-bis [ 4- (4-aminophenoxy)
Phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3
-Aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane or 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane The polyimidesiloxane according to claim 1, which is an aromatic diamine residue (in a total amount of 100 mol% of the diaminopolysiloxane residue and the aromatic diamine residue). 3. Logarithmic viscosity (measured concentration: 0.5 g / 100 ml solvent, solvent: N-methyl-2-pyrrolidone,
The polyimide siloxane according to claim 1, wherein (measured concentration: 30 ° C) is 0.1-3. 4. The polyimidesiloxane according to claim 1, wherein the heat-resistant adhesive can bond various metal foils to the heat-resistant support material at a relatively low temperature.