JP3074661B2 - Polyimide siloxane composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide siloxane solution composition containing a soluble polyimide siloxane, an epoxy resin and a rosin ester. It has excellent properties and storage stability, and can be suitably used for applications such as printing inks and coating varnishes that can form a protective film on a flexible wiring board by screen printing or the like.

The polyimide siloxane composition of the present invention may substantially cause curling when the solution composition is applied to a silicon wafer, a flexible wiring board, etc., and dried and cured to form a protective film. Not
In addition, the protective film has excellent bending resistance and solder resistance (heat resistance), and has adhesion to the substrate, so that it is not necessary to pre-treat the substrate with an adhesion promoter such as a silane coupling agent in advance. Therefore, for example, an excellent protective film can be formed without using the above pretreatment for applications such as passivation films for ICs and LSIs and junction coats for diodes.

[0003]

2. Description of the Related Art Conventionally, the use of an aromatic polyimide, an epoxy resin, or the like as an electrically insulating protective film is, for example, an insulating film for solid-state devices, a passivation film, a semiconductor integrated circuit, an insulating film for a flexible wiring board, or the like. It is known for such uses. In general, epoxy resins require the use of a curing agent in combination, storage stability related to the curing agent,
There are various problems such as workability for two-pack preparation,
Further, when used as the above-mentioned insulating film, there is a problem that the insulating film formed by thermosetting is rigid, lacks flexibility, and is inferior in flexibility.

In general, aromatic polyimide is difficult to dissolve in an organic solvent, so that it is used as a solution of an aromatic polyimide precursor (aromatic polyamic acid) to form a coating film, which is then dried and imidized. And heat treatment at a high temperature for a long time, it is necessary to form a protective film of aromatic polyimide, and there is a problem that the electric or electronic member to be protected is thermally deteriorated.

On the other hand, an aromatic polyimide soluble in an organic solvent is obtained by polymerizing and imidizing a biphenyltetracarboxylic acid and a diamine compound in an organic polar solvent as described in, for example, Japanese Patent Publication No. 57-41491. Aromatic polyimides are known, but the polyimides do not have sufficient adhesion (adhesion) to substrates such as silicon wafers, glass plates, and flexible substrates, so that the substrates are treated in advance with an adhesion promoter. Such a method was necessary.

In order to solve the above-mentioned problems, a precursor of a polyimidesiloxane using diaminopolysiloxane as a diamine component is disclosed in, for example, JP-A-57-1433.
No. 28, and Japanese Patent Application Laid-Open No. 58-13631, these polyimidesiloxane precursors have the disadvantage that the coating film must be treated at a high temperature in order to imidize the polymer. Was.

[0007] Also, Japanese Patent Application Laid-Open No. 61-118424,
JP-A-61-207438, JP-A-63-225
629 and JP-A-1-121325 disclose a soluble polyimide siloxane. However, each of these polyimide siloxanes has several stages in its production process, has a production problem that it takes a long time to produce, does not contain any aromatic diamine as an amine component, and has low heat resistance. The problem that the solubility in various organic solvents is not always sufficient,
When an organic solvent solution of these polyimidesiloxanes is applied on a flexible copper-clad substrate and dried, there is a problem that the adhesion to copper is not sufficient or the flexible substrate is largely curled.

Further, Japanese Patent Application Laid-Open No. 4-36321 discloses that
A solution composition of a soluble polyimide siloxane and an epoxy resin is disclosed. According to this solution composition, the above problem can be solved, but a high temperature (180 ° C. or higher) is required to crosslink the carboxyl group and epoxy group of the polyimide siloxane, and the adhesive is used as an adhesive for a flexible copper-clad substrate. It has an adverse effect and below 180 ° C,
When performing tin plating on copper with an electroless tin plating solution, there has been a problem that the tin plating solution penetrates into a gap between the copper and the protective film due to insufficient adhesion of the protective film to copper.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide high heat resistance, non-curl properties, and adhesion at the same time when a protective film is formed with high solubility in an organic solvent. , A polyimide that has good compatibility with epoxy resin and that epoxy resin acts as a curing agent, and can easily form a protective film having sufficient heat resistance, solvent resistance, and bending resistance. It is to provide a siloxane composition (solution composition).

The present inventors have found that the above object can be achieved by using a polyimide siloxane solution composition comprising a soluble polyimide siloxane, an epoxy resin, and a rosin ester, and have reached the present invention.

[0011]

The present invention provides (a) 2,3,
An aromatic tetracarboxylic acid component containing a 3 ', 4'-biphenyltetracarboxylic acid as a main component;

[0012]

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(Wherein, R 1 represents a divalent hydrocarbon residue, R 2 independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and n represents an integer of 3 to 30.) Is obtained by polymerizing and imidizing 45 to 80 mol% of diaminopolysiloxane, 0.5 to 40 mol% of diaminobenzoic acid, and a diamine component composed of an aromatic diamine having at least two benzene rings. And (c) 2 to 100 parts by weight of a rosin ester, which is uniformly dissolved in an organic polar solvent.

In the present invention, the aromatic tetracarboxylic acid component mainly composed of 2,3,3 ′, 4′-biphenyltetracarboxylic acid includes 2,3,3 ′, 4′-biphenyltetracarboxylic acid, Alternatively, an aromatic tetracarboxylic acid containing 80 mol% or more, particularly 85 to 100 mol%, of biphenyltetracarboxylic acids as esterified products of the acid dianhydride or lower alcohol is used. Of these, especially 2,3,3 ', 4'-
Biphenyltetracarboxylic dianhydride is preferred because it has excellent solubility of the above-mentioned polyimidesiloxane in an organic polar solvent, compatibility with an epoxy compound, and the like.

The aromatic tetracarboxylic acid which can be used together with the above-mentioned biphenyltetracarboxylic acids is 20 mol% or less, especially 15 mol% or less, based on the total tetracarboxylic acid component, for example, 3,3 ′. , 4,4'-biphenyltetracarboxylic acid, 3,3 ', 4,4'-biphenylethertetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid, bis (3,4-dicarboxy Phenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane,
Examples thereof include pyromellitic acid, and acid dianhydrides and esterified products thereof. However, if the amount of these materials is too large, it becomes insoluble in an organic polar solvent or the compatibility with an epoxy compound deteriorates.

In the present invention, as the diaminopolysiloxane represented by the general formula (I), R _{1 in} the formula represents a divalent hydrocarbon group and has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms.
Consists of a plurality of methylene groups or phenylene groups. R ₂ independently represents an alkyl group having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, or a propyl group, or a phenyl group;
0, preferably an integer of 4 to 20. When the number of carbon atoms of R ₁ and R ₂ is too large, or the number of n is too large, the reactivity with the aromatic tetracarboxylic acid component is reduced,
Since the molecular weight of the obtained polyimide siloxane is low, the solubility in an organic solvent is low, and the compatibility with other organic compounds is poor, the above-mentioned degree is appropriate. Examples of specific compounds of diaminopolysiloxane include ω, ω′-bis (2-aminoethyl) polydimethylsiloxane, ω, ω′-bis (3-aminopropyl) polydimethylsiloxane, ω, ω′-bis ( 4-aminophenyl) polydimethylsiloxane, ω, ω'-bis (4-amino-3-methylphenyl) polydimethylsiloxane, ω, ω'-bis
(3-aminopropyl) polydiphenylsiloxane and the like.

In the present invention, examples of the diaminobenzoic acid used together with the diaminopolysiloxane include 3,5-diaminobenzoic acid and 2,6-diaminobenzoic acid, and aromatic rings such as a benzene ring. Aromatic diamine compounds having 2 or more, especially 2 to 5,
Aromatic diamines having two benzene rings such as diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, o-tolidine, o-dianisidine, 1,4-bis (4-amino Phenoxy) benzene, aromatic diamine having three benzene rings such as 1,4-bis (4-aminophenyl) benzene, or bis [4- (4
-Aminophenoxy) phenyl] sulfone, 2,2- [4-
(4-aminophenoxy) phenyl] and aromatic diamines having four benzene rings such as propane.

The diamine component is a diaminopolysiloxane, diaminobenzoic acid, an aromatic diamine having two or more benzene rings, and 10 to the total aromatic diamine.
Aromatic diamines having one benzene ring other than diaminobenzoic acid, such as p-phenylenediamine, m-phenylenediamine, and 2,4-diaminotoluene can be used in combination at a ratio of not more than mol%.

In the present invention, diaminopolysiloxane, diaminobenzoic acid, and an aromatic diamine having two or more benzene rings are contained in an amount of 45 to 80 mol%, 0.5 to 40 mol%, 2 to 60 mol%, and preferably 45 to 80 mol%. ~ 75 mol%, 1
~ 35 mol%, 5 ~ 50 mol%, more preferably 50 ~
75 mol%, 5 to 30 mol%, and 10 to 45 mol% are used. If any one of the components is too large or too small and deviates from these ranges, the resulting polyimide siloxane may have poor solubility in organic solvents, may have poor compatibility with other organic compounds, or may have a flexible wiring. When a protective film is formed on a substrate, the curl becomes large, the heat resistance decreases, and the modulus of elasticity increases.

In the present invention, the polyimide siloxane is obtained by the following method. (1) An aromatic tetracarboxylic acid component and a diaminopolysiloxane and a diamine component of an aromatic diamine are used in approximately equimolar amounts, and are continuously polymerized and imidized at 15 to 250 ° C. in an organic polar solvent to obtain a polyimide. How to get siloxane.

(2) Separating the diamine component, the excess amount of the aromatic tetracarboxylic acid component and diaminopolysiloxane are polymerized and imidized in an organic polar solvent at 15 to 250 ° C. to give an average polymerization degree of 1 Prepare an imidosiloxane oligomer having an acid or acid anhydride group at about 10 to about terminal,
Separately, an aromatic tetracarboxylic acid component and an excess amount of an aromatic diamine are polymerized and imidized in an organic polar solvent at 15 to 250 ° C., and an imide oligomer having an amino group at an end having an average degree of polymerization of about 1 to 10 is obtained. Then, the two are mixed so that the acid component and the diamine component are substantially equimolar and reacted at 15 to 60 ° C.
A method of obtaining a block type polyimide siloxane by raising the temperature to 50 ° C.

(3) The aromatic tetracarboxylic acid component and the diamine component of diaminopolysiloxane and aromatic diamine are used in an approximately equimolar amount, and are first used in an organic polar solvent in an amount of from 20 to 80.
There is a method in which a polyamic acid is once obtained by polymerization at a temperature of ° C and then imidized to obtain a polyimide siloxane.

As the organic polar solvent used for obtaining the above polyimide siloxane, amide solvents such as N,
N-dimethylacetamide, N, N-diethylacetamide,
Solvents containing a sulfur atom such as N, N-dimethylformamide, N, N-diethylformamide, N-methyl-2-pyrrolidone, for example, dimethylsulfoxide, diethylsulfoxide, dimethylsulfone, diethylsulfone, hexamethylsulfonamide, etc. Phenol solvents such as cresol, phenol and xylenol; diglyme solvents such as methyldiglyme and methyltriglyme; solvents having an oxygen atom in the molecule such as acetone;
Examples thereof include organic polar solvents such as methanol, ethanol, ethylene glycol, dioxane, and tetrahydrofuran, and pyridine and tetramethylurea.
If necessary, an aromatic hydrocarbon solvent such as benzene, toluene and xylene, or another organic solvent such as solvent naphtha and benzonitrile may be used in combination.

In the present invention, as the polyimide siloxane, those obtained by any of the above methods (1) to (3) may be used. However, the polyimide siloxane has as high a molecular weight as possible, a high imidization ratio, and an organic polar solvent. At a high concentration of at least 3% by weight or more, preferably 5 to 50% by weight, especially about 5 to 40%, and a solution viscosity at 25 ° C (E-type rotational viscometer) of 0.01%. It is preferably from 1 to 10,000 poise, particularly preferably from 0.1 to 1,000 poise.

The imidization ratio of the polyimide siloxane is 9
The logarithmic viscosity (measurement concentration: 0.5 g / 100 ml, solvent: N-methyl-2-pyrrolidone, measurement temperature: 3) is preferably 0% or more, particularly 95% or more.
0 ° C) is 0.05 to 3, preferably 0.1 to 2. The imidation ratio is measured by an infrared absorption spectrum analysis method.

In the present invention, the epoxy resin to be used is preferably a liquid or powdery epoxy resin having an epoxy equivalent of about 100 to 1,000 and a molecular weight of about 400 to 5,000.
Type and bisphenol F type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd .: Epicoat 1001, 807, etc.), and novolak type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd .: Epicoat 157S-70, Epicoat 1)
52, Epicoat 154, etc.) and glycidylamine type polyfunctional epoxy resin (Epicoat 604, manufactured by Yuka Shell Epoxy Co., Ltd.). A novolak epoxy resin is most preferable from the viewpoint of heat resistance.

In the present invention, the amount of the epoxy resin used is 1 to 100 parts by weight of the polyimide siloxane.
It is 50 parts by weight, preferably 5 to 40 parts by weight. If the amount is too large or too small, the composition gels or the cured film has poor heat resistance and chemical resistance, so the above range is preferable.

In the present invention, as the rosin ester, maleic glycerin ester of abietic acid, glycerin ester of dehydroabietic acid, pentaeristol ester, rosin-modified phenol resin, terpene phenol, glycerin ester of abietic acid and the like are used. It is valid. Polyimide siloxane 10
2 to 100 parts by weight, preferably 5 to 6 parts by weight per 0 parts by weight
0 parts by weight. If the amount is too small, the tin-migration property is deteriorated. Specific examples of the rosin ester include, for example, (1) Arakawa Chemical Co., Ltd.'s trade name Marquid No.1, No.2, No.31 as maleated glycerin ester of abietic acid.
No.100, etc. (2) Arakawa Chemical Co., Ltd. superester A-75, A-100 as glycerin ester or pentaerythritol ester of dehydroabietic acid
, A-115, A-125 etc.,

(3) Tamanol 135, 340, 362, trade names manufactured by Arakawa Chemical Co., Ltd. as rosin-modified phenolic resin
392, etc. (4) Arakawa Chemical Co., Ltd. product name such as Tamanol 803L as terpene phenol, and (5) Arakawa Chemical Co., Ltd. product name ester gum ・ H, 105, 106 as glycerin ester of abietic acid be able to. Among these rosin esters, Marquid
No.31, N0.100, Superester A-75, A-100, A-
115, A-125, ester gum.H, 105, 106 and the like are also preferable from the viewpoint of the stability of the composition.

The composition of the present invention may contain an inorganic filler such as wollastonite, silica and talc, or an inorganic or organic dye or pigment.

In the present invention, the polyimide siloxane solution composition comprises polyimide siloxane, epoxy resin,
And a predetermined amount of rosin ester can be easily obtained by uniformly stirring and mixing. When mixing
It can be mixed in a suitable organic polar solvent to obtain a polyimidesiloxane solution composition. In preparing a solution composition dissolved in a solvent, it may be performed after mixing. The polyimide siloxane may be a polyimide siloxane polymerization solution as it is, or a solution obtained by diluting the polymerization solution with an appropriate organic solvent. Examples of the organic polar solvent include organic polar solvents that can be used when obtaining the polyimide siloxane, and those having a boiling point of 140 ° C or higher are preferable, for example, a boiling point of 180 ° C or higher, particularly 200 ° C.
When the above-mentioned organic polar solvent (for example, methyltriglyme) is used, dissipation due to evaporation of the solvent is extremely reduced, so that storage stability is improved, and screen printing using the printing ink is suitable without any trouble. It is best because it can be done.

The concentration of the polyimide siloxane solution composition is suitably 5 to 50% by weight, preferably 10 to 40% by weight, and the solution viscosity is 0.01 to 10,000 poise, preferably 0.1 to 1000%. Poise is appropriate in terms of workability, physical properties of the solution, and properties of the protective film.

The protective film formed from the polyimidesiloxane composition of the present invention has excellent mechanical strength and electrical insulation, and also has high heat resistance, so that it can be used for various electric or electronic parts (particularly flexible wiring boards). It can be suitably used as a surface protective film or an insulating film. On the surface of the object to be coated (flexible circuit board, semiconductor, etc.), apply it to a uniform thickness by a coating method using a rotary coating machine, a dispenser or a screen printing machine under normal temperature or heating,
By forming a coating film made of the solution composition and then drying the coating film at a temperature of about 110 ° C. or more, particularly about 120 to 180 ° C., a solidified film (protective film, thickness: about 0.1 mm) is formed. (About 5 to 500 μm).

[0034]

The present invention will be described below with reference to examples and comparative examples. The measurement and evaluation in each example were performed by the following methods.

The logarithmic viscosity (η) as a measure of the molecular weight of the polyimide siloxane is determined by uniformly dissolving the polyimide siloxane in N-methyl-2-pyrrolidone so that the concentration becomes 0.5 g / 100 ml, and using a Canon fence. Solution viscosity and solvent N-methyl
The viscosity of 2-pyrrolidone was measured at 30 ° C. and calculated by the following equation.

[0036]

(Equation 1)

The imidization ratio of polyimide siloxane (%)
Is about 95% as measured by infrared absorption spectrum analysis.
Above, especially 95 to 100%, substantially "amide-
Those having no "acid bond" are preferred.

[Production of Polyimide Siloxane] Reference Example 1 In a glass flask having a capacity of 2 liters, 294.22 g of 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride and 700 g of methyltriglyme were charged. Ω, ω'-bis (3-aminopropyl) polydimethylsiloxane (X-2, manufactured by Shin-Etsu Silicon Co., Ltd.)
2-161AS, n = 9) 605.3 g and triglyme 655 g were added and uniformly dissolved.
The polymerization was carried out for 4 hours while maintaining the temperature by heating to 85 ° C. Then, the reaction solution was returned to room temperature and stirred,
2-bis [4- (4-aminophenoxy) phenyl] propane 6
After adding 2.2 g and 23.05 g of 3,5-diaminobenzoic acid, the reaction temperature was raised to 185 ° C., and the mixture was further reacted for 4 hours to prepare a polyimidesiloxane solution. The polyimide siloxane thus obtained had a yield of 99%, a logarithmic viscosity of 0.20 as a measure of molecular weight, and an imidization ratio of substantially 100%.

[Electroless tin plating boring test method] Thickness 3
7μm thick copper foil (Nippon Mining Co., LP-6)
5 μm polyethylene terephthalate spacer (1
0 mm × 200 mm), and the polyimide siloxane solution composition was cast on the spacer, and 8 mm on a heating plate.
The coating was dried and heated at 0 ° C. for 30 minutes and at 150 ° C. for 60 minutes to be cured, thereby forming a protective film of a polyimidesiloxane solution composition. A 150 μm pattern was printed on the copper surface (the surface opposite to the side on which the protective film was formed) with a commercially available etching resist (SER-420, manufactured by Yamaei Chemical), and cured at 120 ° C. for 30 minutes. This at a temperature of 50 °
After etching in a ferric chloride aqueous solution of C (60 Baume) for 10 to 15 minutes, a 2% aqueous sodium hydroxide solution
The etching resist was peeled off by immersion for 3 minutes. The copper pattern on the polyimidesiloxane film thus obtained is electroless tin-plated (580M, manufactured by Ishihara Chemical Co., Ltd.)
After immersion in a bath at 70 ° C. for 30 minutes, silicone oil (KF-965, manufactured by Shin-Etsu Silicon Co., Ltd.) at 260 ° C.
-100 CS) for 30 seconds. The degree of tin digging is determined by utilizing the fact that the tin digging portion turns black when immersed in thermal silicone oil. That is, by taking a photograph in which the tin plating solution reaches the interface between the copper and the polyimidesiloxane composition at a magnification of 36 times, the tin drilling width (μm) is measured and determined. Tin hole width 14
A test result of less than 15 μm passes this test, and a test result of 15 μm or more fails.

[Flexibility] Polyimide film of 75 μm (made by Ube Industries, Ltd .; trade name: Upilex S-75)
A polyimide siloxane solution composition is cast thereon so that the film thickness after heat treatment becomes 20 to 30 μm, pre-dried at 80 ° C. for 30 minutes, and heat-treated at 150 ° C. for 60 minutes to form a coating film I do. Bend so that the coating surface is on the outside,
The peak of the bent portion was observed with a microscope of 50 times to determine the presence or absence of a crack. ○: no crack, Δ: whitened portion of the bent portion, ×:
Evaluate as cracked.

[Solder Heat Resistance] A copper foil having a thickness of 35 μm (LP-6, manufactured by Nikko Co., Ltd.)
The solution composition of the polyimide siloxane was cast so as to have a thickness of 30 μm, and was preliminarily dried at 80 ° C. for 30 minutes.
C. heat treatment for 60 minutes to produce a coating film. After preparing a 3 x 5 cm coated plate and contacting and cooling the coated surface in a molten solder bath at 260 ° C for 30 seconds, a cross-cut peel test was performed. , Δ: Slight peeling, ×: Peeling.

[Preparation of Polyimide Soloxane Solution Composition] Example 1 7.20 g of novolak type epoxy resin (Epicoat 157S-70, manufactured by Yuka Shell Epoxy Co., Ltd.) and maleated abietic acid were added to 100 g of the polyimidesiloxane solution of Reference Example 1. Glyceride (Arakawa Chemical; Marquid No.100)
2.34 g was charged into a 500 ml glass flask and stirred at room temperature (25 ° C.) for 2 hours to obtain a uniformly dissolved polyimidesiloxane solution composition (solution viscosity: 120 poise). Using this solution composition, the above-mentioned tin burring test, flexibility, and solder heat resistance were examined. This solution composition maintained a uniform solution state and viscosity even after being left at room temperature for one week. The results are shown in Table 1.

Examples 2 to 4 The maleated abietic acid glyceride of Example 1 was
Except having changed to the amount of a table, it carried out similarly to Example 1, and
A solution composition of polyimide siloxane was manufactured, and a tin-migration test, a bending property, and a solder heat resistance were examined. The results are shown in Table 1.

Examples 5 to 8 The maleic abietic acid glyceride of Example 1 was replaced with pentaerythritol ester of dehydroabietic acid (manufactured by Arakawa Chemical Co .; superester A-115) and the amounts shown in Table 1 were used. In the same manner as in Example 1, a solution composition of polyimide siloxane was produced, and the tin-migration test, the flexibility, and the solder heat resistance were examined. The results are shown in Table 1.

[0045]

[Table 1]

Comparative Example 1 Nothing was added except that 7.20 g of a novolak type epoxy resin (Epicoat 157S-70, manufactured by Yuka Shell Epoxy Co., Ltd.) was added to the solution composition of polyimide siloxane obtained in Reference Example 1. A solution composition of polyimide siloxane was produced in the same manner as in Example 1, and the change in viscosity, tin-migration test, flexibility, and solder heat resistance were examined. However, in the tin-migration test, the black color was easily formed due to insufficient adhesion between the protective film and copper. The results are shown in Table 1.

[0047]

According to the present invention, the polyimide siloxane composition containing the soluble polyimide siloxane, epoxy resin and rosin ester is excellent in heat resistance, adhesion, chemical resistance and storage stability, and can be used on a flexible wiring board. In addition, the present invention relates to uses such as printing inks and coating varnishes capable of forming a protective film by screen printing or the like. The polyimide siloxane composition of the present invention does not substantially cause curling when the solution composition is applied to a silicon wafer, a flexible wiring board, and the like, and dried and cured to form a protective film. The protective film has excellent bending resistance and solder resistance (heat resistance), and also has excellent adhesion to the substrate, and it is not necessary to pre-treat the substrate with an adhesion promoter such as a silane coupling agent. ,
For example, an excellent protective film can be formed for applications such as passivation films for ICs and LSIs and junction coats for diodes without performing the above pretreatment.

Continuation of front page (56) References JP-A-5-140524 (JP, A) JP-A-5-32950 (JP, A) JP-A-5-25453 (JP, A) JP-A-5-140525 (JP) JP-A-5-25452 (JP, A) JP-A-4-364796 (JP, A) JP-A-4-36321 (JP, A) JP-A-6-157874 (JP, A) 5-9437 (JP, A) JP-A-4-298093 (JP, A) JP-A-4-23833 (JP, A) JP-A-1-121325 (JP, A) (58) Fields investigated (Int. Cl ^7, DB name) C08G 59/40 -. 59/58 C08L 79/08 C08L 63/00 - 63/10

Claims (1)

(57) [Claims] 1. An aromatic tetracarboxylic acid component comprising (a) 2,3,3 ′, 4′-biphenyltetracarboxylic acid as a main component,
General formula (I) (Wherein, R ₁ in the formula is a divalent hydrocarbon group, R ₂
Independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and n represents an integer of 3 to 30. ) Is obtained by polymerizing and imidizing 45 to 80 mol% of the diaminopolysiloxane, 0.5 to 40 mol% of diaminobenzoic acid, and a diamine component comprising an aromatic diamine having at least two benzene rings. A polyimide siloxane composition, wherein 100 parts by weight of the obtained soluble polyimide siloxane, (b) 1 to 50 parts by weight of an epoxy resin, and (c) 2 to 100 parts by weight of a rosin ester are uniformly dissolved in an organic polar solvent.