JPH04108879A - Polyimide resin coating agent composition - Google Patents

Abstract

PURPOSE:To obtain the title composition useful for coating film for cord, cable, etc., semiconductor protecting film, insulating film, coating compound, etc., having excellent heat resistance, mechanical characteristics, adhesiveness and electrical characteristics, containing a specific polyimide resin soluble in organic solvents and an organic solvent. CONSTITUTION:The objective composition comprising (A) a polyimide resin obtained by subjecting (i) 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride and/or 4,4'-(hexafluoroisopropylidene)diphthalic acid dianhydride and (ii) a diamine component consisting of 50-99mol% aromatic diamine shown by formula I [X is single bond, O, S, SO2, CO, CH2, C(CH3)2 or C(CF3)2-] and 1-50mol% siloxane-based diamine shown by formula II (R1 and R2 are bifunctional organic group; R3 to R6 are alkyl, phenyl, etc.; (n) is 1-50 integer) to polycondensation to give a polyimide and (B) an organic solvent such as ether-based or amide- based organic solvent.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention has excellent heat resistance, mechanical properties, and is soluble in organic solvents.
The present invention also relates to a new coating agent composition containing a polyimide resin with excellent adhesiveness and electrical properties, and more specifically, it is useful for coats, coating films for cables, etc., protective films for semiconductors, insulating films, paints, etc. The present invention relates to a polyimide resin coating composition.

[Conventional technology]

Polyimide resin has various excellent properties such as heat resistance, mechanical properties, and chemical resistance, and is widely used as an industrial material mainly in electronic materials. In addition, in recent years, many developments have been made in silicon-modified polyimide resins, which are copolymers with silicon compounds, in order to add electrical properties, adhesive properties, plasma resistance properties, etc. to the properties of these polyimide resins. It is widely used in the electronic industry as a protective film and an insulating film (Japanese Patent Application Laid-open No. 60-76, 5
33, JP-A No. 62-223.228, etc.).

However, polyimide resin is generally insoluble in organic solvents, and when used, it is generally necessary to form a film or apply it with polyamic acid, which is its precursor, and then perform an imidization reaction by heating etc. to form a polyimide resin coating. It is being done.

However, when imidization is performed after film formation or coating with polyamic acid, water is generated due to the ring-closing reaction of polyamic acid, creating voids within the film, and the film and film must be imidized at high temperatures. There were problems such as thermal damage to the formed substrate, metal, etc. Furthermore, there is a problem in that the film obtained by imidizing polyamic acid does not have satisfactory adhesive strength.

As a means to solve such problems, for example,
USP 3,325,450, USP 3,740,
It is also possible to use solvent-soluble polyimide resins that are soluble in solvents such as those disclosed in No. 305, but these solvent-soluble polyimide resins do not have sufficient coating strength;
Since the glass transition point is also low, there is a problem that it cannot withstand use at high temperatures.

The present inventors have already developed a patent application for a different purpose.
No. 4 and Japanese Unexamined Patent Publication No. 2-91.125 propose polyimide resins containing solvent-soluble systems. We have continued to study the applications of these polyimide resins.

[Problem to be solved by the invention]

Therefore, the object of the present invention is to obtain a target object that has excellent heat resistance, mechanical properties, adhesive properties, and electrical properties by simply removing the solvent without requiring imidization treatment after film formation and coating. An object of the present invention is to provide a polyimide resin coating composition.

[Means to solve the problem]

That is, the present invention provides a polyimide resin coating agent composition containing at least a polyimide resin and an organic solvent, in which the polyimide resin is 3°3', 4.4'
-diphenylsulfonetetracarboxylic dianhydride and/or
or 4.4'-(hexafluoroisopropylidene)diphthalic dianhydride and the following general formula ((However, in the formula, X does not exist or -〇S--SO□--CO-1-CH
2--C(CH3)2- or C(Ch)2-) and the following general formula (n) R= Rs (However, in the formula, R1 and R2 are Indicates a divalent organic group, R3-
R6 represents an alkyl group, a phenyl group, or a substituted phenyl group, and n represents an integer of 1 to 50. This is a polyimide resin coating agent composition which is an organic solvent-soluble polyimide resin obtained by imidizing a precursor.

The polyimide resin used in the present invention is synthesized from an aromatic carboxylic dianhydride and a diamine component. And, as such aromatic carboxylic dianhydride, 3.3'
, 4,4'-diphenylsulfonetetracarboxylic dianhydride and/or 4,4''-(hexafluoroisopropylidene)diphthalic dianhydride are used.

In addition, as a diamine component, the following general formula (I) (I) (However, in the formula, X does not exist or -〇s--5o
2- -co-1-CH2--C(CH3)2- or C
(CF3)2-) is used. Specifically, such aromatic diamines include 2,2-bis-[4-(4-aminophenoxy)phenyl-1propane, 2,2-bis-[4-(3-aminophenoxy)phenyl-1propane] , bis[4-(4-aminophenoxy)phenyl 1 sulfone, bis-[4-(3
aminophenoxy) phenyl 1 sulfone, 2,2 bis-
[4-(4-aminophenoxy)phenyl 1 hexafluoropropane, 2,2-bis-[4-(3-aminophenoxy)phenyl 1 hexafluoropropane, bis[4
-(4-aminophenoxy)1biphenyl, bis[4-
(3-aminophenoxy)1biphenyl, bis[1(4
-aminophenoxy) 1-biphenyl, bis[1-(3-aminophenoxy)]biphenyl, bis[4-(4-aminophenoxy)phenyl 1methane, bis[4-(3-aminophenoxy)phenyl 1methane, bis[4- (4aminophenoxy)phenyl 1 ether, bis[4-(
3-Aminophenoxy)phenyl]ether, bis[4
-(4-aminophenoxy)]benzophenone, bis[
Examples include 4-(3-aminophenoxy)1benzophenone. These may be used alone or in combination of two or more.

Furthermore, as the other diamine component, the following general formula (n
) R3R5 H2N-R++5i-0+-V-3! -R2NH2R4
R6(n) (However, in the formula, R1 and R2 represent a divalent organic group, and R3-
A siloxane diamine represented by R6 represents an alkyl group, a phenyl group, or a substituted phenyl group, and n represents an integer of 1 to 50 is also used as an essential copolymerization component.

Such siloxane diamines include CH3CH3 82N-(CH2)3÷5i-Oh--3i-(CH2
)3-NH2CH3CH3 CH3CH3 82N-(CH2)a+5i-0+T-3i-(CH2
)4-NH2CH3CH3 ph ph H2N-(CH2)3 +S i-0'h-3i-(C
H2) 3-NH2Ph Ph ph ph H2N-(CH2)4÷5i-0+T-3i-(CH2
)4-NH2ph ph etc. These siloxane diamines have a weight average molecular weight of 200 to 5,000, preferably 200 to 3,000. These may be used alone or in combination of two or more.

In addition to the above-mentioned essential copolymerization components, other copolymerization components may be introduced into the polyimide resin used in the present invention, as long as the solubility in organic solvents and its various properties are not impaired. Examples of the copolymerizable aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3
．． 3', 4.4'-biphenyltetracarboxylic dianhydride, 2.3', 4.4'-biphenyltetracarboxylic dianhydride, 3.3', 4.4'-benzophenonetetracarboxylic acid Dianhydride, 3.3'.

4.4'-diphenyl ether tetracarboxylic dianhydride, 2.3', 4.4'-diphenyl ether tetracarboxylic dianhydride, 2.3.6.7-naphthalene tetracarboxylic dianhydride, 1.2 .5.6-naphthalenetetracarboxylic dianhydride, 1.4.5.8-naphthalenetetracarboxylic dianhydride, 2,2'-bis(3,4
-dicarboxyphenyl)propanihydride, 2.2'
-bis(2,3-dicarboxyphenyl)propanihydride, 1'bis(2,3-dicarboxyphenyl)ethane dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 2.3.6.7-anthracenetetracarboxylic dianhydride, 1.2.7.8-phenanthrenetetracarboxylic dianhydride, 3.4.9.1.0-perylenetetracarboxylic dianhydride 4,4-bis(2,3
-dicarboxyphenyl)diphenylmethane dianhydride, etc. can be used.

In addition, other copolymerizable aromatic diamines include:
For example, m-phenylenediamine, p-phenylenediamine, 4.4'-diaminodiphenylpropane, 4.4'
-diaminodiphenylmethane, 4,4"-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4.4'-diaminodiphenyl sulfide, 4.4
'-Diaminodiphenylsulfone, 2゜6-diamitupyridine, bis(4-aminophenyl)phorphine oxide, bis(4-aminophenyl)N-methylamine, ■
, 5-diaminonaphthalene, 3,3”dimethyl-4,4
″-diaminobiphenyl, 3,3′-dimethoxybenzidine, 2,4-bis(β-amino-tert-butyl)
Examples include toluene, bis(p-β-amino-tertbutylphenyl)ether, p-bis(2-methyl-4aminopentyl)benzene, and the like.

The polyimide resin used in the present invention may be a random copolymer obtained by reacting an aromatic tetracarboxylic dianhydride with an aromatic diamine and a siloxane diamine in a polar solvent in one step, or a diamine component and an aromatic copolymer. A block copolymer may be obtained by reacting a group tetracarboxylic dianhydride in two steps and having an imide bonding unit composed of each diamine as a block structure. The block copolymer obtained by such a two-step reaction generally has a microphase-separated structure, and by including both units in the molecular structure, when used in the polyimide resin coating agent composition of the present invention, the resulting coating film exhibits excellent properties in strength, heat resistance, and adhesion.

The polyimide resin used in the present invention contains the aromatic tetracarboxylic dianhydride and the diamine component in a polar solvent at a molar ratio of 0.9 to 1.1, preferably in the range of 0.95 to 1.05, and at a reaction temperature of 0. It can be produced by reacting at ~100[deg.] C. for 0.5 to 10 hours, and then converting the resulting polyamic acid, which is a polyimide precursor, into reimidization through dehydration and ring closure. Further, in order to control the degree of polymerization, it is also possible to add a terminal capping agent such as phthalic anhydride, nadic anhydride, maleic anhydride, aniline, benzoyl chloride, and the like. The polyimide resin obtained in this way is made of, for example, N
- Logarithmic viscosity measured in an organic solvent such as methyl-2-pyrrolidone at a polymer concentration of 0.5 g/di and a temperature of 30°C is 0.1 to 5.0 dl/g, preferably 0.2 to 3.
．． 0dl! /g.

Examples of organic solvents used in polymerization reactions include diethylene glycol dimethyl ether (diglyme).
, diethylene glycol diethyl ether, ether solvents such as tetrahydrofuran, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, Examples include phenolic solvents such as phenol, cresol, chlorophenol, and xylenol.

These solvents can be used alone, and
It can also be used as a mixed solvent in which two or more types are combined.

In addition, as a method for imidizing polyamic acid, which is a polyimide precursor, by dehydration and ring closure to obtain a polyimide resin, it can be carried out by a known method such as the following in-solution thermal imidization method, chemical imidization method, or direct imidization method. .

(1) In-solution thermal imidization method Imidization is carried out by heating the polyimide precursor in a solution to 100° C. or higher, preferably 130° C. or higher. At this time, benzene, toluene, xylene,
A solvent such as N-cyclohexyl-2-pyrrolidone is preferably used, and a tertiary amine such as triethylamine, pyridine, N,N-dimethylaniline may be added as a reaction accelerator.

(2) Chemical imidization method A fatty acid anhydride such as acetic anhydride or propionic anhydride is added as a dehydrating agent to the polyimide precursor solution, and imidization is performed at room temperature or under heating. At this time, it may be added as the tertiary amine reaction accelerator.

(3) Direct imidization method The polyimide precursor is precipitated in a poor solvent such as water, methanol, hexane, etc. that does not dissolve the polyimide precursor,
Imidization is performed by heating the powdered polyimide precursor obtained after isolation to a temperature of 100°C or higher, preferably 150°C or higher.

The polyimide resins obtained in this way include N,N dimethylformamide, N,N-dimethylacetamide, N-
Since it is completely soluble in polar solvents such as methyl-2-pyrrolidone, N-cyclohexyl 2-pyrrolidone, and dimethyl sulfoxide, the polyimide resin after imidization can be dissolved in these solvents and used as a coating composition, or
Alternatively, the solvent used in the polymerization reaction can be used as is as a coating solvent without removing it.

The polyimide resin coating agent composition of the present invention can be given properties by adding various additives depending on the purpose. Such additives include those within the range that do not impair the solubility of diethylene glycol dimethyl ether (diglyme), ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), and their acetate derivatives. Flowability improvers to improve fluidity, wear resistance improvers such as graphite and molybdenum disulfide, fiber reinforcing agents such as glass fiber, carbon fiber, and whiskers, magnesium carbonate, calcium carbonate, antimony trioxide, etc. Examples include flame retardancy improvers, electrical property improvers, oxidation stabilizers, fillers such as silica, alumina, titania, zirconia, and talc, pigments, and dyes.

〔Example〕

Examples of the present invention will be shown below to explain the present invention in more detail.

The abbreviations used in each example are as follows.

DSDA: 3.3°, 4.4'-diphenylsulfonetetracarboxylic dianhydride 6FBDA: 4.4'-(hexafluoroisopropylidene)diphthalic dianhydride BTDA: 3.3', 4.4'- Benzophenone tetracarboxylic dianhydride BPDA: 3.3', 4.4''-biphenyltetracarboxylic dianhydride PMDA: Pyromellitic dianhydride BAPP: 2.2-bis(4-aminophenoxyphenyl)propane BAPS : Bis(4-aminophenoxyphenyl) sulfone BAPB : Bis(4-aminophenoxy)biphenyl BAPF : 2.2-bis(4-aminophenoxyphenyl)hexafluoropropane BAPE : Bis(4-aminophenoxyphenyl) ether DADE : 4.4'-diaminodiphenyl ether NMP: N-methyl-2-pyrrolidone DMAc: N, N-dimethylacetamide DIG
Nidiethylene glycol dimethyl ether THF:
For tetrahydrofuran and siloxane diamines, the following abbreviations were used depending on the average molecular weight.

FSX248: average molecular weight 248 PSX480: 480 PSx740: 1740 PSX1240: 1240 Example 1 BPDA 35°8 in a 0.5A' separable flask
g (0.1 mol) was dispersed in DMAc200-, then FSX740-15, 0 g (0.0203
A solution prepared by dissolving mol) in 50 g of old G was gradually added dropwise under water cooling, and after the dropwise addition was completed, the reaction was further carried out at 30°C for 2 hours. Furthermore, BAPE32. 72 g (0,0797 mol) was dissolved in 200 ml of DMAc and gradually added dropwise to the above reaction solution, and after completion of the dropwise addition, the mixture was stirred and reacted for 12 hours to obtain a polyamic acid solution.

Next, after adding 50 d of toluene to this solution, 150 d of toluene was added.
The mixture was heated to ℃ and subjected to dehydration and ring closure under refluxing toluene to obtain a polyimide solution.

This solution was spin-coded onto the surfaces of silicon, copper, aluminum, silica, and alumina substrates, and solvent-dried at 100° C. for 30 minutes and at 200° C. for 60 minutes to form coating films. This coating film was tough and showed good adhesion.

Examples 2 to 10 Using the same method as in Example 1, soluble polyimides were synthesized with the compositions shown in Table 1, and solubility and coating film performance tests were conducted.

Table 1 shows the properties of the synthesized polyimide solution, and Table 2 shows the performance of the formed coating film.

Comparative Examples 1 to 3 Using the same method as in Example 1 without using DSDA and 6FBDA at all, polyimides were synthesized with the compositions shown in Table 1, and solubility and coating film performance tests were conducted.

Table 1 shows the properties of the synthesized polyimide solution, and Table 2 shows the performance of the formed coating film.

〔Effect of the invention〕

The polyimide resin coating composition of the present invention is soluble in organic solvents, has excellent moldability, does not require imidization treatment after coating, has high heat resistance, excellent mechanical properties, and has excellent adhesive properties. Because of its excellent electrical properties, it can be used as coating materials for cords, cables, etc., protective films for semiconductors, insulating films and films,
Useful for adhesives, paints, etc.

Patent applicant: Nippon Steel Chemical Co., Ltd.

Claims (2)

[Claims] (1) In a polyimide resin coating agent composition containing at least a polyimide resin and an organic solvent, the polyimide resin contains 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride and/or 4,4' -(Hexafluoroisopropylidene)diphthalic dianhydride and the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, in the formula, X does not exist, or -O-, - S-
, -SO_2-, -CO-, -CH_2-, -C(CH
___3) 50 to 99 mol% aromatic diamine represented by ___2- or -C(CF_3)_2-) and the following general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (However, In the formula, R_1 and R_2 represent a divalent organic group, and R
_3 to R_6 represent an alkyl group, a phenyl group, or a substituted phenyl group, and n represents an integer of 1 to 50) obtained by polycondensing a diamine component consisting of 1 to 50 mol% of a siloxane diamine 1. A polyimide resin coating agent composition, which is an organic solvent-soluble polyimide resin obtained by imidizing a polyimide precursor. (2) The polyimide resin coating according to claim 1, wherein the organic solvent is at least one solvent selected from the group consisting of ether solvents, amide solvents, phenol solvents, and dimethyl sulfoxide. agent composition.