JPH07258410A - Polyimide siloxane - Google Patents

Abstract

(57) [Abstract] [Purpose] Solubility in organic solvents, heat resistance and chemical resistance as well as electrical insulation make it possible to protect surface and interlayer insulation films of electrical and electronic parts, and between copper foil and substrate. It can be used as an adhesive component. An aromatic tetracarboxylic acid component containing 3,3 ′, 4,4′-biphenyltetracarboxylic acid as a main component, 45 to 85 mol% of diaminopolysiloxane, and an aromatic diamine having a plurality of aromatic rings 15 to 15 It is obtained by polymerizing and imidizing a diamine component consisting of 55 mol%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface protective film for electric / electronic parts which has solubility, heat resistance, chemical resistance and electrical insulation properties, an interlayer insulating film, and an adhesive component between a copper foil and a substrate. The present invention relates to a special polyimide siloxane useful as.

[0002]

2. Description of the Related Art Conventionally, aromatic polyimide has been used as a main component of an electrically insulating protective film and a heat resistant adhesive, for example, as an interlayer insulating film of a flexible wiring board, a semiconductor integrated circuit or a copper foil. Various applications have already been known for applications such as adhesive compositions between substrates. However,
In general, aromatic polyimide is not dissolved in an organic solvent, so it is used as a solution of a precursor of aromatic polyimide (aromatic polyamic acid), and then the coating film is dried and imidized at a high temperature for a long time. Therefore, it is necessary to form a protective film, and there is a problem that the electrical or electronic member itself to be protected is thermally deteriorated. On the other hand, Japanese Patent Publication No. 57-41491 discloses aromatic polyimide soluble in an organic solvent, but since the adhesiveness with a silicon wafer, a glass plate, a flexible wiring substrate, etc. is not sufficient, the substrate, etc. are attached in advance. A method such as treatment with an accelerator was necessary.

In order to solve the above-mentioned problems, a precursor of polyimidesiloxane using diaminopolysiloxane as a diamine component is disclosed in, for example, JP-A-57-1433.
No. 28 and JP-A No. 58-13631, the precursors of these polyimidesiloxanes have the drawback that they must be treated at high temperature for imidization.

Further, JP-A-61-118424, JP-A-61-207438 and JP-A-63-2256.
No. 29 and JP-A-1-121325 disclose soluble polyimide siloxanes. However, these polyimidesiloxanes have a problem that the manufacturing process involves several steps, and that it takes a long time to manufacture, or does not include an aromatic diamine as a diamine component at all,
There are problems that the heat resistance is low, that the solubility in various organic solvents is not always sufficient, and that when the flexible wiring substrate is applied and dried, the substrate largely curls.

Further, the soluble polyimide siloxane disclosed in JP-A-4-23833 and JP-A-4-36321 is an adhesive composition between an interlayer insulating film of a flexible wiring substrate, a semiconductor integrated circuit or the like, or a copper foil and a substrate. When used for such purposes, there was a problem that it was dissolved in the washing process using acetone in the manufacturing process.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyimide siloxane which has high solubility and heat resistance in a specific low boiling point solvent, good chemical resistance, and easy manufacturing process. It is to be.

[0007]

[Means for Solving the Problems] The inventors of the present invention have conducted diligent research for the purpose of improving the above problems, and
Aromatic tetracarboxylic acid component containing 3 ', 4,4'-biphenyltetracarboxylic acid as a main component, diaminopolysiloxane 45 to 85 mol% and aromatic diamine having a plurality of aromatic rings 15 to 55 mol% Polyimide siloxane obtained by polymerizing and imidizing a diamine component has high solubility and heat resistance in a specific low boiling point solvent, and also has good chemical resistance, and its manufacturing process is easy. I came to this invention.

This invention relates to (a) an aromatic tetracarboxylic acid component containing 3,3 ', 4,4'-biphenyltetracarboxylic acid as a main component and a general formula (1).

[0009]

[Chemical 2]

(Wherein R represents a divalent hydrocarbon residue, R ₁ , R ₂ , R ₃ and R ₄ represent a lower alkyl group or a phenyl group, and n represents an integer of 3 to 40). (B) polymerizing and imidizing a diamine component consisting of 45 to 85 mol% of diaminopolysiloxane represented by the formula) and 15 to 55 mol% of aromatic diamine having a plurality of aromatic rings. Characteristic polyimide siloxane.

In the present invention, the proportion of the aromatic tetracarboxylic acid component containing biphenyltetracarboxylic acids as the main component is 30 mol% or less, particularly 25 mol% or less,
Other aromatic tetracarboxylic acid components that can be used together with 3,3 ′, 4,4′-biphenyltetracarboxylic acid include 2,3,3 ′, 4′-biphenyltetracarboxylic acids and 3,3 ′. ,
4,4'-Benzophenonetetracarboxylic acids, 3,3 ', 4,4'-
Biphenyl ether tetracarboxylic acids, pyromellitic acids, etc. are used. Among these, especially 2,3,3 ',
4′-biphenyltetracarboxylic dianhydride is preferable because it is excellent in solubility of the polyimidesiloxane in an organic polar solvent, compatibility with an epoxy compound, and the like.

In the present invention, examples of the aromatic tetracarboxylic acid component that can be used together with the biphenyl tetracarboxylic acids include, for example, 3,3 ', 4,4'-benzophenone tetracarboxylic acid, 3,3', 4, 4'-diphenyl ether tetracarboxylic acid, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, pyromellitic acid, or their acid dianhydrides or ester compounds And the like can be preferably mentioned. However, if the amount of these used is too large, the polyimide siloxane becomes insoluble in the organic polar solvent or the compatibility with the epoxy resin deteriorates, which is not suitable.

In the present invention, as the diaminopolysiloxane represented by the general formula (1), R in the formula is a "plurality of methylene groups" having 2 to 6 carbon atoms, particularly 3 to 5 carbon atoms, or a phenylene group. R ₁ is a divalent hydrocarbon residue
~ R ₄ has 1 carbon atom such as methyl group, ethyl group, propyl group, etc.
It is preferable that it is a lower alkyl group or phenyl group of 5 to 5, and n is an integer of 4 to 20, particularly 5 to 20, and more preferably 5 to 15. R, R
_If the carbon number of _{1 to} R ₄ is too large, or the number of n is too large, the reactivity and heat resistance deteriorate, the molecular weight of the resulting polyimidesiloxane decreases, and the solubility in organic solvents decreases. Or, the compatibility with other organic compounds may deteriorate, so that the above-mentioned level is suitable.

Specific examples of the diaminopolysiloxane represented by the general formula (1) include ω, ω'-bis (2-aminoethyl) polydimethylsiloxane and ω, ω'-bis (3
-Aminopropyl) polydimethylsiloxane, ω, ω '
-Bis (3-aminobutyl) polydimethylsiloxane,
ω, ω'-bis (3-aminopropyl) polymethylphenylsiloxane, ω, ω'-bis (4-aminophenyl) polydimethylsiloxane, ω, ω'-bis (4-amino-3-
Methylphenyl) polydimethylsiloxane, ω, ω'-
Suitable examples include bis (3-aminopropyl) polydiphenylsiloxane and the like.

The aromatic diamine used together with the diaminopolysiloxane is generally an aromatic diamine compound having two or more aromatic rings such as benzene rings, especially 2 to 5 aromatic rings, such as biphenyl-based diamine compounds and diphenyl ether. Diamine compounds, benzophenone diamine compounds, diphenyl sulfone diamine compounds,
Diphenylmethane-based diamine compound, diphenylpropane-based diamine compound, diphenylthioether-based diamine compound, bis (phenoxy) benzene-based diamine compound, bis (phenoxyphenyl) sulfone-based diamine compound, bis (phenoxy) diphenylsulfone-based diamine compound, bis (phenoxyphenyl) ) Hexafluoropropane-based diamine compounds, bis (phenoxyphenyl) propane-based diamine compounds, and the like,
They can be used alone or as a mixture.

Specific examples of the aromatic diamine include diphenyl ether type diamine compounds such as 4,4′-diaminodiphenyl ether and 3,3′-diaminodiphenyl ether, 1,3-bis (3-aminophenoxy) benzene,
Bis (phenoxy) benzene-based diamine compounds such as 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane, 2,2-bis [4-
(3-Aminophenoxy) phenyl] propane and other bis (
(Phenoxyphenyl) propane-based diamine compound, bis
[4- (4-aminophenoxy) phenyl] sulfone, bis
Aromatic diamine compounds having 2 to 5 aromatic rings, such as bis (phenoxyphenyl) sulfone-based diamine compounds such as [4- (3-aminophenoxy) phenyl] sulfone, can be preferably mentioned.

In the polyimidesiloxane of the present invention, the former amount of the diaminopolysiloxane and the aromatic diamine is 45 to 85 mol%, preferably 45 to 80 mol%, more preferably 45 to 75 mol%, and the latter is 15 to 55 mol%. %, Preferably 20 to 55 mol%, more preferably 25
Used in a proportion of ˜55 mol%. If either component is too little or too much and is out of these ranges, the solubility of the polyimide siloxane in an organic solvent will decrease, the compatibility with other organic compounds will deteriorate, and on a flexible wiring board. It is not suitable because it greatly curls when a protective film is formed on it, or the heat resistance, mechanical properties, etc. decrease.

In the present invention, the component (a) polyimide siloxane is produced by the following method. (A ₁ ) Aromatic tetracarboxylic acid component and diamine polysiloxane and diamine component of aromatic diamine are used in approximately equimolar amounts to continuously polymerize and imidize in an organic polar solvent at a temperature of 15 to 250 ° C. To obtain polyimide siloxane.

(A ₂ ) The diamine component is divided, and first, an excess amount of the aromatic tetracarboxylic acid component and diaminopolysiloxane are polymerized and imidized in an organic polar solvent at a temperature of 15 to 250 ° C. to obtain an average polymerization. 1-30, preferably about 1-20, an imide siloxane oligomer having an acid or acid anhydride group at the terminal is prepared, and an aromatic tetracarboxylic acid component and an excess amount of aromatic diamine are separately added in an organic polar solvent. Polymerization and imidization are carried out at a temperature of 15 to 250 ° C. to prepare an imide oligomer having an amino group at the terminal with an average degree of polymerization of 1 to 30, preferably about 1 to 20, and then both of these are acid and diamine components. And are mixed so as to be approximately equimolar and reacted at a temperature of 15 to 60 ° C, and further heated to 130 to 250 ° C to form a block type polyimide siloxane. How to get.

(A ₃ ) Aromatic tetracarboxylic acid components, diaminopolysiloxane and aromatic diamine components are used in approximately equimolar amounts, and first in an organic polar solvent at a temperature of 20 to 80 °.
There is a method of polymerizing with C to obtain a polyamic acid once and then imidizing it to obtain a polyimidesiloxane.

Examples of the organic polar solvent used for producing the polyimidesiloxane in the present invention include N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, Amide solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, solvents containing sulfur atoms such as hexamethyl sulfolamide, cresol, phenol, phenolic solvents such as xylenol, Acetone, methanol,
Examples thereof include solvents having an oxygen atom in the molecule such as ethanol, ethylene glycol, dioxane, and tetrahydrofuran, and other solvents such as pyridine and tetramethylurea. Furthermore, if necessary, benzene, toluene,
It is also possible to use together an aromatic hydrocarbon solvent such as xylene, another type of organic solvent such as solvent naphtha, and benzonitrile.

In the present invention, the polyimide siloxane may be obtained by any method such as (a ₁ ) to (a ₃ ) described above, but it is as high molecular weight as possible and has a high imidization ratio, and is an organic polar solvent. At least 3% by weight or more, especially 5
What can be dissolved at a high concentration of about 40% by weight is preferable because a laminated plate having good laminating operation and laminating performance can be obtained.

The imidization ratio of polyimidesiloxane is 90 as measured by infrared absorption spectroscopy.
% Or more, particularly 95% or more is preferable, and in the infrared absorption spectrum analysis, the absorption peak related to the amide-acid bond of the polymer is not substantially found and only the absorption peak related to the imide ring bond is observed, and the imidization ratio is high. It is preferable.

Polyimide siloxane has a logarithmic viscosity (measurement concentration: 0.5 g / 100 ml solution, solvent: N-methyl-2-pyrrolidone, measurement temperature:
30 ° C, viscometer: Canon Fenske type viscometer)
It is suitable to be about 0.05 to 3, especially about 0.10 to 2.

The present invention will be described in detail below with reference to Examples and Comparative Examples. The solubility of polyimide siloxane is
Add 0.2 g of polyimidesiloxane powder to 0.8 g of tetrahydrofuran and acetone at 20 ° C., and let it stand and observe the dissolution state. When dissolved within 1 hour, ◎ When dissolved within 1 day ◯, evaluation was made as Δ when simply swelling in the solvent, and x when completely insoluble even in one week.

Example 1 A glass flask having a capacity of 2 liters equipped with a thermometer, a charging / discharging outlet and a stirrer was charged with N-methyl-2-pyrrolidone (
NMP) 1000g, then 3,3 ', 4,4'
-Biphenyltetracarboxylic dianhydride (s-BPD
A) 73.56 g (250 mmol), ω, ω'-bis (3-aminopropyl) polydimethylsiloxane (Toray
Dow Corning Silicone, BY16-853
U; DAPS) 132 g (150 mmol), 2,2
-Bis [4- (4-aminophenoxy) phenyl] propane (BAPP) 41.05 g (100 mmol) was charged, and the temperature was raised to 60 ° C in a nitrogen stream, and at this temperature 3
Reacted for hours. Then, the reaction solution was heated to 200 ° C. and reacted at that temperature for 3 hours. The reaction liquid cooled to room temperature was added to 10 liters of water, and the polymer precipitated in 30 minutes using a homomixer was filtered to isolate the polymer powder, and the polymer powder was dissolved in 5 liters of water. It was washed twice for 15 minutes using a homomixer and dried in hot air at 120 ° C. for 5 hours to obtain 220 g of polyimidesiloxane powder. The obtained polyimide siloxane had an inherent viscosity (30 ° C.) of 0.26 and an imidization ratio of substantially 100%.

Example 2 NMP 500 g, 2,3,3 ', ^4' -biphenyltetracarboxylic dianhydride (a-BPDA) 29.25 in a 1 liter capacity glass flask under a nitrogen atmosphere.
g (100 mmol) and BAPP 82.11 g (20
0 mmol) was added, and the mixture was reacted at 60 ° C. for 2 hours. Further, the temperature was raised to 200 ° C. and polymerization was carried out for 3 hours while removing water to synthesize a diamine-terminated imide oligomer (YO component). Further, 500 g of NMP was placed in a glass flask having a capacity of 1 liter, and then s-
BPDA 88.27 g (300 mmol), DAPS
After charging 176 g (200 mmol), the temperature was raised to 60 ° C. in a nitrogen stream and the reaction was carried out at this temperature for 2 hours. Next, the reaction solution was heated to 200 ° C. and reacted at that temperature for 3 hours while removing water to synthesize an acid-terminated imide oligomer (X1 component). Next, in a glass flask having a capacity of 2 liters, 100 g of NMP and 10 parts of YO component were added.
7.93 g (100 mmol) and X1 component 257 g
(100 mmol) was added, and the mixture was reacted under nitrogen at 60 ° C. for 2 hours and further heated at 200 ° C. for 3 hours while removing water. Finally, the reaction solution was cooled to room temperature, added to 10 liters of water, and a polymer was precipitated using a homomixer for 30 minutes. The polymer was filtered, and the polymer powder was isolated. Perform 15 minutes of washing twice in 1 liter of water using a homomixer.
It was dried with hot air at 20 ° C. for 5 hours to obtain 340 g of polyimidesiloxane powder. The obtained polyimidesiloxane had an inherent viscosity (30 ° C.) of 0.24 and an imidization ratio of substantially 100%.

Examples 3 to 4 and Comparative Examples 1 to 6 The same as Example 1 except that the types and amounts (molar ratios) shown in Table 1 were used as the aromatic tetracarboxylic acid component and the diamine component. , Polyimide siloxane (the imidization ratio is substantially 95% or more) were manufactured. The solubility of these polyimidesiloxanes is shown in Table 1.

[0029]

[Table 1]

[0030]

EFFECT OF THE INVENTION Since the polyimide siloxane of the present invention is a flexible polymer having a constitutional unit based on diaminopolysiloxane in a considerably high proportion, it retains heat resistance, electrical properties and mechanical properties, and It has excellent solubility in organic solvents (especially solubility in methyl diglyme and tetrahydrofuran), and also shows excellent chemical resistance to acetone and methanol used in the washing process of electric and electronic parts. It is a thing.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenji Sonoyama 3-10 Nakamiyakitamachi, Hirakata City, Osaka Prefecture Ube Industries Ltd. Hirakata Laboratory

Claims (1)

[Claims] 1. An aromatic tetracarboxylic acid component comprising (a) 3,3 ′, 4,4′-biphenyltetracarboxylic acid as a main component and a general formula (1): (However, R in the formula represents a divalent hydrocarbon residue, and R ₁ ,
R _2, R ₃ and R ₄ represents a lower alkyl group or a phenyl radical, n aromatic diamine having a diamino polysiloxane 45 to 85 mol% and more aromatic ring represented by shows an integer of 3 to 40) A polyimidesiloxane obtained by (b) polymerizing and imidizing a diamine component consisting of 15 to 55 mol%.