JP3275722B2 - 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 barium sulfate. Excellent in chemical properties (especially solder flux resistance, tin plating solution resistance) and storage stability, and suitable for applications such as printing inks and coating varnishes that can form a protective film on flexible wiring boards by screen printing etc. Used for

The polyimidesiloxane composition of the present invention does not 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. In addition, the protective film has excellent bending resistance and heat resistance (for example, solder heat resistance), has adhesion to a substrate, and is pre-treated with an adhesion promoter such as a silane coupling agent in advance. Therefore, an excellent protective film can be formed.

[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.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to have high solubility in an organic solvent and, when a protective film is formed, simultaneously have high heat resistance, non-curlability and adhesion. In addition, it has good compatibility with epoxy resin and does not adversely affect adhesives, etc., and has sufficient heat resistance, chemical resistance (especially solder flux resistance, tin plating liquid resistance), and bending resistance It is an object of the present invention to provide a polyimide siloxane composition (solution composition) that can easily form a protective film having the following.

[0007]

That is, the present invention provides:
(A) General formula (1)

[0008]

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General formula (2)

[0010]

Embedded image And the general formula (3)

[0011]

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(Wherein R1 represents a tetravalent residue obtained by removing tetracarboxylic acid from aromatic tetracarboxylic acid;
R2 represents a divalent residue excluding the amino group of the diaminopolysiloxane of the general formula (4), and R3 represents a divalent residue excluding the amino group from the aromatic diamine compound represented by the general formula (5). , R4 represents a divalent residue excluding an amino group from a diamine compound other than the diamine compounds represented by the general formulas (4) and (5); n1 represents 3 to 30;
Represents a divalent hydrocarbon group or a phenyl group; R6 independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group;
× represents a direct bond or a general formula (6), r1 represents a hydroxyl group or a carboxyl group, n2 represents an integer of 1 or 2, n3 represents an integer of 0 to 3, R7 and R8 represent hydrogen or a methyl group. Or a halogenated methyl group, and the proportion of m1, m2 and m3 is 45 to 9
5 mol%, m2 is 0.5 to 40 mol%, and m3 is the balance. ) General formula (4)

[0013]

Embedded image General formula (5)

[0014]

Embedded image General formula (6)

[0015]

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(B) 1 to 50 parts by weight of an epoxy resin, and (C) 2 to 150 parts by weight of barium sulfate.
When the protective film is formed on a copper foil, the protective film thickness becomes 20 μm.
Immersion in a tin plating bath at 70 ° C for 5 minutes
The present invention relates to a polyimide siloxane composition for a protective film of an electronic component, which does not discolor .

Further, the present invention relates to (a) general formula (1)

[0018]

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General formula (2)

[0020]

Embedded image And the general formula (3)

[0021]

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(Wherein R1 represents a tetravalent residue obtained by removing tetracarboxylic acid from aromatic tetracarboxylic acid;
R2 represents a divalent residue excluding the amino group of the diaminopolysiloxane of the general formula (4), and R3 represents a divalent residue excluding the amino group from the aromatic diamine compound represented by the general formula (5). , R4 represents a divalent residue excluding an amino group from a diamine compound other than the diamine compounds represented by the general formulas (4) and (5); n1 represents 3 to 30;
Represents a divalent hydrocarbon group or a phenyl group; R6 independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group;
× represents a direct bond or a general formula (6), r1 represents a hydroxyl group or a carboxyl group, n2 represents an integer of 1 or 2, n3 represents an integer of 0 to 3, R7 and R8 represent hydrogen or a methyl group. Or a halogenated methyl group, and the proportion of m1, m2 and m3 is 45 to 9
5 mol%, m2 is 0.5 to 40 mol%, and m3 is the balance. ) General formula (4)

[0023]

Embedded image General formula (5)

[0024]

Embedded image General formula (6)

[0025]

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(B) 1 to 50 parts by weight of an epoxy resin, and (C) 2 to 150 parts by weight of barium sulfate.
When the protective film is formed on a copper foil, the protective film thickness becomes 20 μm.
Immersion in a tin plating bath at 70 ° C for 5 minutes
The present invention relates to a cured product for a protective film of an electronic component, which is obtained by heating a polyimidesiloxane composition that does not discolor .

The polyimidesiloxane in the present invention includes aromatic tetracarboxylic dianhydride or a derivative thereof (such as an ester), a diaminopolysiloxane represented by the general formula (4) and a diamine compound represented by the general formula (5) Can be obtained by thermal imidization or chemical imidization in an organic solvent.

In the present invention, the aromatic tetracarboxylic acid includes 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-diphenylethertetracarboxylic acid, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 2,2-bis ( 3,4-benzenedicarboxylic acid) hexafluoropropane, pyromellitic acid, 1,4-bis (3,4-benzenedicarboxylic acid)
80 mol% or more of benzene, 2,2-bis [4- (3,4-phenoxydicarboxylic acid) phenyl] propane, or their anhydrides or esterified lower alcohols,
In particular, aromatic tetracarboxylic acids containing 85 to 100 mol% are used. Of these, 2,3,
3 ′, 4′-biphenyltetracarboxylic acid, 3,3 ′,
4,4'-Diphenylethertetracarboxylic acid is preferred because the polyimidesiloxane has excellent solubility in organic solvents.

In the present invention, as the diaminopolysiloxane represented by the general formula (4), R5 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. R6 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, and n1 represents 3 to 3
0, preferably 3 to 20. If the number of n1 is small, the curl property is increased, which is not preferable. If the number of n1 is too large, the chemical resistance is lowered, the reactivity with the aromatic tetracarboxylic acid component is reduced, or the like. Since the molecular weight of the resulting 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 α, ω-bis (2-aminoethyl) polydimethylsiloxane and α, ω-bis (3-aminopropyl)
Polydimethylsiloxane, α, ω-bis (4-aminophenyl) Polydimethylsiloxane, α, ω-bis (4-aminophenyl)
Amino-3-methylphenyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydiphenylsiloxane, α, ω-bis (4-aminobutyl) polydimethylsiloxane, and the like.

In the present invention, examples of the diamine compound represented by the general formula (5) include benzenecarboxylic acids such as 3,5-diaminobenzoic acid and 2,4-diaminobenzoic acid, and 3,3′-diamino, 4,4. 4′-dihydroxybiphenyl, 4,4′-diamino, 3,3′-dihydroxybiphenyl, 4,4′-diamino, 2,2′-dihydroxybiphenyl, 4,4′-diamino, 2,
Hydroxybiphenyl compounds such as 2 ′, 5,5′-tetrahydroxybiphenyl, 3,3′-diamino,
4,4'-dicarboxybiphenyl, 4,4'-diamino, 3,3'-dicarboxybiphenyl, 4,4'-diamino, 2,2'-dicarboxybiphenyl, 4,4 '
Carboxybiphenyl compounds such as -diamino, 2,2 ', 5,5'-tetracarboxybiphenyl;
3'-diamino, 4,4'-dihydroxydiphenylmethane, 4,4'-diamino, 3,3'-dihydroxydiphenylmethane, 4,4'-diamino, 2,2'-
Dihydroxydiphenylmethane, 2,2-bis [3-
Amino, 4-hydroxyphenyl] propane, 2,2
-Bis [4-amino, 3-hydroxyphenyl] propane, 2,2-bis [3-amino, 4-hydroxyphenyl] hexafluoropropane, 4,4'-diamino, 2,2 ', 5,5'- Hydroxydiphenylalkane compounds such as tetrahydroxydiphenylmethane, 3,3′-diamino, 4,4′-dicarboxydiphenylmethane, 4,4′-diamino, 3,3′-dicarboxydiphenylmethane, 4,4′-diamino, 2,
2'-dicarboxydiphenylmethane, 2,2-bis [3-amino, 4, -carboxyphenyl] propane,
2,2-bis [4-amino, 3-carboxyphenyl]
Carboxydiphenylalkane compounds such as propane, 2,2-bis [3-amino, 4-carboxyphenyl] hexafluoropropane, 4,4′-diamino, 2,2 ′, 5,5′-tetracarboxybiphenyl, 3 ,
3′-diamino, 4,4′-dihydroxydiphenyl ether, 4,4′-diamino, 3,3′-dihydroxydiphenyl ether, 4,4′-diamino,
2'-dihydroxydiphenyl ether, 4,4'-
Hydroxydiphenyl ether compounds such as diamino, 2,2 ', 5,5'-tetrahydroxydiphenyl ether; 3,3'-diamino, 4,4'-dicarboxydiphenyl ether; '-Diamino, 3,3'
-Dicarboxydiphenyl ether, 4,4'-diamino, 2,2'-dicarboxydiphenyl ether, 4,
Carboxydiphenyl ethers such as 4'-diamino, 2,2 ', 5,5'-tetracarboxydiphenyl ether
Ter compounds, 3,3'-diamino, 4,4'-dihydroxydiphenylsulfone, 4,4'-diamino,
3,3′-dihydroxydiphenyl sulfone, 4,
4'-diamino, 2,2'-dihydroxydiphenylsulfone, 4,4'-diamino, 2,2 ', 5,5'-
Hydroxydiphenylsulfone compounds such as tetrahydroxydiphenylsulfone, 3,3′-diamino,
4,4'-dicarboxydiphenyl sulfone, 4,4 '
-Diamino, 3,3'-dicarboxydiphenylsulfone, 4,4'-diamino, 2,2'-dicarboxydiphenylsulfone, 4,4'-diamino, 2,2 ', 5
Carboxydiphenylsulfone compounds such as 5′-tetracarboxydiphenylsulfone, 2,2-bis [4
Bis (hydroxyphenoxyphenyl) alkane compounds such as-(4-amino, 3-hydroxyphenoxy) phenyl] propane and bis such as 2,2-bis [4- (4-amino, 3-carboxyphenoxy) phenyl] propane (Carboxyphenoxyphenyl) alkane compounds, bis (hydroxyphenoxy) biphenyl compounds such as 4,4′-bis (4-amino, 3-hydroxyphenoxy) biphenyl, and 4,4′-bis (4
Bis (carboxyphenoxy) biphenyl compounds such as -amino, 3-carboxyphenoxy) biphenyl,
Bis (hydroxyphenoxyphenyl) sulfone compounds such as 2,2-bis [4- (4-amino, 3-hydroxyphenoxy) phenyl] sulfone; and 2,2-bis [4- (4-amino, 3-carboxyphenoxy) ) Phenyl] sulfone and the like, and bis (carboxyphenoxyphenyl) sulfone compounds.

In the present invention, R4 represented by the general formula (3) is a diamine compound (H ₂ N—R4-N) other than the diamine compounds represented by the general formulas (4) and (5).
H ₂ ) represents a divalent residue from which an amino group has been removed. As the diamine compound (H ₂ N—R 4 —NH ₂ ), 1,4
-Diaminobenzene, 1,3-diaminobenzene, 2,
Diamines containing one benzene such as 4-diaminotoluene, 1,4-diamino, 2,5-dihalogenobenzene, bis (4-aminophenyl) ether, bis (3-
Aminophenyl) ether, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone,
Bis (4-aminophenyl) methane, bis (3-aminophenyl) methane, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfide, 2,2
-Bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) propane, 2,2-bis (4-
Aminophenyl) hexafluoropropane, o-dianisidine, o-tolidine, diamines containing two benzenes such as tolidinesulfonic acids, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-amino Phenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,4-bis (3-aminophenyl) benzene, α, α′-bis (4-aminophenyl) -1,
Diamines containing three benzenes, such as 4-diisopropylbenzene and α, α′-bis (4-aminophenyl) -1,3-diisopropylbenzene, 2,2-bis [4-
(4-aminophenoxy) phenyl] propane, 2,2
-Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4 '-(4-aminophenoxy) biphenyl, 9, Diamine compounds such as diamines containing four or more benzenes, such as 9-bis (4-aminophenyl) fluorene and 5,10-bis (4-aminophenyl) anthracene. Aliphatic diamine compounds such as hexamethylenediamine and diaminododecane can be used together with the above diamines.

In the present invention, the units of the general formula (1), the general formula (2) and the general formula (3) in the polyimidesiloxane component are 45 to 95 mol% and 0.5 to 95 mol%, respectively.
-40 mol% and the balance, preferably 45-95 each
Mol%, 1 to 40 mol%, 0 to 50 mol%, more preferably 45 to 95 mol%, 5 to 35 mol%,
It is used in a proportion of 45 mol%. 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 heat resistance. Is not suitable because it decreases.

The polyimidesiloxane of the present invention can be obtained, for example, by the following method. (1) Polyimide siloxane obtained by polymerizing and imidizing an aromatic tetracarboxylic acid component and a diamine component of diaminopolysiloxane and aromatic diamine in an organic polar solvent at 15 to 250 ° C. continuously in substantially equimolar amounts. How to get.

(2) Separating the diamine component, an excess amount of the aromatic tetracarboxylic acid component and diaminopolysiloxane are polymerized and imidized in an organic polar solvent at 15 to 250 ° C. Prepare an imidosiloxane oligomer having an acid or acid anhydride group at about 10 terminals,
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. to give an imide oligomer having an amino group at an end having an average degree of polymerization of about 1 to 10. The acid component and the diamine component are mixed so as to be substantially equimolar and reacted at 15 to 60 ° C.
A method of obtaining a block type polyimide siloxane by raising the temperature to 0 ° C.

(3) The aromatic tetracarboxylic acid component and the diamine component of diaminopolysiloxane and aromatic diamine are used in approximately equimolar amounts, and are first used in an organic polar solvent in an amount of from 20 to 8%.
There is a method in which a polyamic acid is once obtained by polymerization at 0 ° C. and then imidized to obtain a polyimide siloxane.

As the organic polar solvent used for obtaining the above-mentioned polyimidesiloxane, nitrogen-containing solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N- Diethylformamide, N-methyl-2-pyrrolidone,
Solvents containing a sulfur atom such as 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, and the like, phenol solvents such as dimethylsulfoxide, diethylsulfoxide, dimethylsulfone, diethylsulfone, and hexamethylsulfonamide; Diglyme solvents such as cresol, phenol and xylenol; solvents having an oxygen atom in the molecule such as diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), and tetraglyme; acetone, methanol, ethanol, ethylene glycol, dioxane; Other examples include pyridine, tetramethylurea, and the like. 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 least 3% by weight,
It can be dissolved at a high concentration of preferably 5 to 60% by weight, particularly about 5 to 55%, and has a solution viscosity at 25 ° C (E-type rotational viscometer) of 0.01 to 10,000 poise, particularly 0 It is preferably from 1 to 1,000 poise.

The imidation ratio of the polyimide siloxane is 9
0% or more, particularly 95% or more is preferable, and the logarithmic viscosity (measurement concentration: 0.5 g / 100 ml, solvent: N-methyl-2-pyrrolidone, measurement temperature: 30)
C) is 0.05 to 3, preferably 0.1 to 2.

The epoxy resin used in the present invention (hereinafter may be simply referred to as epoxy) is a liquid or solid epoxy resin having an epoxy equivalent of about 100 to 1000 and a molecular weight of about 300 to 5000. Resins are preferred. For example, epoxy resins of bisphenol A type or bisphenol F type (made by Yuka Shell: Epicoat 806, Epicoat 825, etc.), and trifunctional or higher epoxy resins (made of Yuka Shell: Epicoat 152, Epicoat 154, Epicoat 180 series) Epicoat 157 series, Epicoat 1032 series, manufactured by Ciba Geigy: MT0163, etc.).

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 used is too large or too small, the composition gels or the heat resistance and chemical resistance after curing deteriorate, so the above range is preferable.

In addition to the epoxy resin, additional components such as hydrazides and imidazoles which promote the curing of the epoxy resin may be used.

The barium sulfate used in the present invention may have any size and form, but may have an average particle diameter of 0.1 to 25 μm (for example, B-30 manufactured by Sakai Chemical Industry Co., Ltd.). , B-54).
It is not preferable to use a material out of this range, since cracks are generated when the obtained coating film is bent or the bent portion is whitened.

In the present invention, the amount of barium sulfate used is 2 to 100 parts by weight of the polyimide siloxane.
The amount is 150 parts by weight, preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight, and particularly preferably 15 to 80 parts by weight. If the amount is too large or too small, cracks occur due to bending of the coating film, heat resistance and discoloration of the copper foil deteriorate, so the above range is preferable.

A silicon-based thickening component such as Aerosil (finely powdered silica) manufactured by Nippon Aerosil is preferably used in an amount of 1 to 100 parts by weight of polyimide siloxane.
It is preferable to add 50 parts by weight, especially 5 to 40 parts by weight.

In the present invention, the polyimidesiloxane solution composition can be easily obtained by uniformly stirring and mixing a predetermined amount of each of the polyimidesiloxane, the epoxy resin, and the barium sulfate. When mixing
It can be mixed in a suitable organic 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 solvent include an organic polar solvent that can be used when obtaining the above-mentioned polyimide siloxane, and a solvent having a boiling point of 140 ° C or higher is preferable. The use of triglyme is optimal since the dissipation by evaporation of the solvent is greatly reduced and the storage stability is improved.

The concentration of the polyimide siloxane solution composition is 5 to 60% by weight, preferably 5 to 55% by weight,
Among them, 10 to 55% by weight is appropriate, and the above solution viscosity is preferably 0.01 to 10000 poise, preferably 0.1 to 1000 poise in terms of workability, physical properties of the solution, and properties of the protective film. Suitable from.

The protective film formed from the polyimidesiloxane composition of the present invention has excellent mechanical strength and electrical insulation, and also has heat resistance and chemical resistance (solder flux resistance, tin plating solution resistance). Therefore, it can be suitably used as a surface protective film or an interlayer insulating film of various electric or electronic components (particularly, flexible wiring boards). On the surface of the object to be coated (flexible circuit board, semiconductor, etc.)
At room temperature or under heating, a spin coater, a uniform thickness is applied by a coating method using a dispenser or a printing machine to form a coating film made of the solution composition, and then the coating film is heated to 50 ° C. or higher, Preferably about 110 ° C. or higher, especially 120 ° C.
By drying at a temperature of about 180 ° C., a solidified film (protective film, thickness: about 0.5 to 500 μm) can be formed.

[0049]

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 compounds used in each of the following examples are shown below together with their abbreviations. a-BPDA: 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride BTDA: 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride PMDA: pyromellitic dianhydride ETDA: 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride DSDA: 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride 6FDA: 2,2-bis (3,3 4-benzenedicarboxylic anhydride) hexafluoropropane PSI: α, ω-bis (3-aminopropyl) polydimethylsiloxane DABA: 3,5-diaminobenzoic acid HAB: 3,3′-dihydroxy-4,4 '-Diaminobiphenyl MBAA: bis (3-carboxy, 4-aminophenyl) methane MBHA: bis (3-hydroxy, 4-aminophenyl) methane FF: 2,2-bis (4-hydroxy, 3-aminophenyl) hexafluoropropane DADE: 4,4'-diaminodiphenyl ether TPEQ: 1,4- (4-aminophenoxy) benzene BAPP: 2,2 -Bis [4- (4-aminophenoxy) phenyl] propane TG: triglyme NMP: N-methyl-2-pyrrolidone

[Measurement of Logarithmic Viscosity (ηinh)] The logarithmic viscosity (ηinh) of the polyimidesiloxane reaction solution can be expressed by the following equation. ηinh = ln (t / t ₀ ) / c, where t is the transit time (seconds) between the marked lines in the Cannon-Fenske viscometer of the measurement solution, and t ₀ is the distance between the marked lines in the Cannon-Fenske viscometer of the pure solvent. The transit time (seconds), c represents the concentration of solid polyimidesiloxane (g / 100 ml solvent). The viscosity was measured at 30 ° C. and N-methyl-2-
The test was carried out using a pyrrolidone solvent at a polyimide siloxane solid concentration of 0.5 g / 100 ml.

[Measurement Method of Average Particle Diameter] The average particle diameter of barium sulfate was determined by observation with an electron microscope. The barium sulfate used was B-30 (average particle diameter: 0.3 μm) manufactured by Sakai Chemical Industry, and B-54 (average particle diameter: manufactured by the company).
1.2 μm).

[Method of Measuring Solder (Solder) Heat Resistance] A polyimide spacer having a thickness of 50 μm was placed on a glossy surface of an electrolytic copper foil having a thickness of 35 μm, and a polyimide siloxane mixture (composition) was cast. 30 minutes at 80 ° C, 60 minutes at 160 ° C
After heating and drying for a minute, a protective film of a polyimidesiloxane mixture was formed. The copper foil on which the polyimide siloxane protective film is formed is cut into 3 × 3 cm, and a rosin-based flux (SUNFLUX SF-27 manufactured by Sanwa Chemical Industry Co., Ltd.) is placed on the protective film.
After coating 0), the surface of the protective film was contacted with a molten solder bath at 260 ° C. for 30 seconds, and after cooling, the presence or absence of blistering of the protective film was observed and evaluated. ○: no blistering, △: slight blistering, ×: blistering

[Method of Measuring Discoloration of Copper Foil] A 75 μm-thick polyimide spreadsheet was formed on the glossy surface of a 35 μm-thick electrolytic copper foil.
The polyimide siloxane mixture (composition) was cast using a server and dried by heating at 80 ° C. for 30 minutes and at 160 ° C. for 60 minutes. A copper foil on which a protective film of a polyimidesiloxane mixture having an uneven thickness of 5 to 40 μm
It was cut into a size of × 10 cm and immersed in a tin plating bath (Tipposit LT-34, Shipley Fast East Co., Ltd.) heated to 70 ° C. for 5 minutes. Thereafter, the substrate was washed with hot water of 70 ° C. or higher for 5 minutes and dried. 5-40 μm
A part of the copper foil on the side on which the polyimide siloxane protective film having a thickness of 3 mm was formed was partially discolored. When the thickness of the protective film in the discolored portion was less than 20 μm, it was judged as ○, and when it was 20 μm or more, it was judged as ×.

[Adhesion] A spacer was placed on the rough surface of an electrolytic copper foil having a thickness of 35 μm or on a polyimide film having a thickness of 75 μm.
The mixture (composition) of the polyimide siloxane is cast using, for example, and dried by heating at 80 ° C. for 30 minutes and at 150 ° C. for 60 minutes.
A protective film of 0 to 30 μm was formed. JIS D for protective film
A 1 mm wide cut is made according to
After forming the grids, an adhesive tape was adhered thereon, and the adhesive tape was peeled off. The percentage of the number of grids not peeled was indicated by%.

[Flexibility] A polyimide siloxane mixture (composition) was cast on a 75 μm-thick polyimide film using a spacer or the like, and the mixture was heated at 80 ° C. for 30 minutes for 15 minutes.
Heat drying was performed at 0 ° C. for 60 minutes to form a protective film having a polyimide siloxane mixture film thickness of 20 to 30 μm. The polyimide film was bent so that the protective film face was on the outside, and the peak of the bent portion was observed under a microscope of 50 times to determine the presence or absence of a crack. ○: No crack at all, △: Bleached part whitened, ×: Cracked

[Production of Polyimide Siloxane] Reference Example 1 In a 20-liter glass flask, 2, 3,
3 ', 4'-biphenyltetracarboxylic dianhydride 2
94.22 g and triglyme 700 g were charged and dissolved with stirring at room temperature, and then α, ω-bis (3-aminopropyl) polydimethylsiloxane (Shin-Etsu Silicon,
X-22-161AS, n = 9) 605.30 g and triglyme 185 g were added and uniformly dissolved, and the mixture was heated to 185 ° C. under a nitrogen atmosphere and polymerized for 4 hours while maintaining this temperature. Then, the reaction solution was returned to room temperature and stirred with 2,2-bis [4- (4-aminophenoxy).
After adding 62.20 g of [phenyl] propane, 23.05 g of 3,5-diaminobenzoic acid and 509 g of triglyme, the reaction temperature was raised to 185 ° C., and the mixture was further reacted for 4 hours to prepare a polyimidesiloxane solution. This imidosiloxane had a concentration of 40.5% by weight and a solution viscosity of 21 poise. The polyimide siloxane thus obtained has a yield of 99%, a logarithmic viscosity of 0.23 as a measure of molecular weight, and an imidization ratio of substantially 100%.
Met.

Reference Example 2 In a glass flask having a capacity of 500 ml, a-BPDA4 was added.
4.1 g (150 mmol) and 100 g of triglyme were charged and heated at 180 ° C. with stirring in a nitrogen atmosphere. α,
77.7 g of ω-bis (3-aminopropyl) polydimethylsiloxane (amino equivalent 370, n = 7.6) and 50 g of triglyme were added, and the mixture was heated at 180 ° C. for 60 minutes.
Further, 3.4 g of DABA and BAPP9.
After adding 2 g and 36 g of triglyme, the mixture was heated and stirred at 180 ° C. for 6 hours, and then filtered. The resulting polyimide siloxane reaction solution had an imidosiloxane solid content concentration of 41%.
It was a homogeneous solution having a weight% of ηinh of 0.28 and a solution viscosity of 40 poise. The imidation ratio was substantially 100%.

Reference Examples 3 to 31 A polyimide siloxane reaction liquid shown in Table 1 was obtained in the same manner as in Reference Example 2, except that the acid dianhydride and the diamine component shown in Tables 1 and 6 were used. Only Reference Example 21 is 100
This was performed using a 0 ml glass container.

Example 1 In a glass container, 100 g of the polyimidesiloxane solution obtained in Reference Example 1, 7.20 g of an epoxy resin (Epicoat 157S-70, manufactured by Yuka Shell Co., Ltd.) and barium sulfate 2
0.0 g (manufactured by Sakai Chemical Industry Co., Ltd .: B-30, average particle size: 0.
3 μm) 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 solder heat resistance, discoloration of copper foil, flexibility, and adhesion were measured. This solution composition maintained a uniform solution state and viscosity even after being left at room temperature for one week. Table 2 shows the results.

Examples 2 to 43 In the same manner as in Example 1 except that the polyimide siloxane reaction solution, epoxy resin and barium sulfate of the types and amounts shown in Tables 2, 3 and 7 were used, the solution composition of the polyimide siloxane was used. Was manufactured. The solder heat resistance, the copper foil discoloration, the flexibility, and the adhesion were measured, respectively. Tables 2 and 3 show the results.
And Table 7 below.

Comparative Examples 1 to 38 A polyimidesiloxane solution composition was prepared in the same manner as in Example 1 except that the components and the amounts shown in Tables 4, 5 and 8 were used. The solder heat resistance, the copper foil discoloration, the flexibility, and the adhesion were measured, respectively. The results are shown in Tables 4, 5 and 8.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

[Table 4]

[0067]

[Table 5]

[0068]

[Table 6]

[0069]

[Table 7]

[0070]

[Table 8]

[0071]

The polyimide siloxane composition containing the soluble polyimide siloxane, epoxy resin and barium sulfate according to the present invention has heat resistance, adhesion, chemical resistance (particularly solder flux resistance, tin plating solution resistance) and Excellent storage stability.

The cured product obtained by heating the polyimide siloxane composition of the present invention has excellent bending resistance and heat resistance (for example, solder heat resistance), and has good adhesion to substrates such as copper and polyimide films. Excellent, can be formed as an excellent protective film without pre-treatment of the substrate in advance with an adhesion promoter such as a silane coupling agent.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-36321 (JP, A) JP-A-5-156226 (JP, A) JP-A-8-253677 (JP, A) JP-A-7- 304950 (JP, A) JP-A-8-333455 (JP, A) JP-A-6-200216 (JP, A) JP-A-4-298093 (JP, A) JP-A-6-157875 (JP, A) JP-A-6-157874 (JP, A) Yoshikazu Abe et al., New edition, plastics combination agent-basics and applications, Taiseisha Co., Ltd., Japan, January 30, 1984, pp. 111-112 (58) ) Surveyed field (Int.Cl. ⁷ , DB name) C08G 59/40 C08L 79/08 C08L 63/00-63/10 C08K 3/30

Claims (2)

(57) [Claims] (1) (a) General formula (1) General formula (2) And the general formula (3) (However, R1 in the formula represents a tetravalent residue excluding the tetracarboxylic acid from the aromatic tetracarboxylic acid, and R2 represents a divalent residue excluding the amino group of the diaminopolysiloxane of the general formula (4). , R3 represent a divalent residue excluding an amino group from the aromatic diamine compound represented by the general formula (5);
4 represents a divalent residue excluding the amino group from the diamine compound excluding the diamine compounds represented by the general formulas (4) and (5), n1 represents 3 to 30, and R5 represents a divalent hydrocarbon. A phenyl group or a phenyl group;
X represents an alkyl group or a phenyl group; X represents a direct bond or a general formula (6); r1 represents a hydroxyl group or a carboxyl group; n2 represents an integer of 1 or 2;
R7 and R8 each represent a hydrogen, a methyl group or a halogenated methyl group, and the proportions of m1, m2 and m3 are 45 to 95 mol%,
Is 0.5 to 40 mol% and m3 is the balance. ) General formula (4) General formula (5) General formula (6) Organic solvent soluble polyimide siloxane 10 represented by
0 parts by weight, (b) 1 to 50 parts by weight of epoxy resin and (C) 2 to 150 parts by weight of barium sulfate , on copper foil
When the protective film thickness is 20 μm, 70
A polyimide siloxane composition for a protective film of an electronic component, wherein the copper foil does not discolor even when immersed in a tin plating bath at 5 ° C. for 5 minutes . (A) General formula (1) General formula (2) And the general formula (3) (However, R1 in the formula represents a tetravalent residue excluding the tetracarboxylic acid from the aromatic tetracarboxylic acid, and R2 represents a divalent residue excluding the amino group of the diaminopolysiloxane of the general formula (4). , R3 represent a divalent residue excluding an amino group from the aromatic diamine compound represented by the general formula (5);
4 represents a divalent residue excluding the amino group from the diamine compound excluding the diamine compounds represented by the general formulas (4) and (5), n1 represents 3 to 30, and R5 represents a divalent hydrocarbon. A phenyl group or a phenyl group;
X represents an alkyl group or a phenyl group; X represents a direct bond or a general formula (6); r1 represents a hydroxyl group or a carboxyl group; n2 represents an integer of 1 or 2;
R7 and R8 each represent a hydrogen, a methyl group or a halogenated methyl group, and the proportions of m1, m2 and m3 are 45 to 95 mol%,
Is 0.5 to 40 mol% and m3 is the balance. ) General formula (4) General formula (5) General formula (6) Organic solvent soluble polyimide siloxane 10 represented by
0 parts by weight, (b) 1 to 50 parts by weight of epoxy resin and (C) 2 to 150 parts by weight of barium sulfate , on copper foil
When the protective film thickness is 20 μm, 70
A cured product for a protective film of an electronic component, which is obtained by heating a polyimidesiloxane composition without discoloring the copper foil even after immersion in a tin plating bath at 5 ° C. for 5 minutes .