JPH04108880A - 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 O, 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, amide-based or phenol-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.
In addition, regarding a new coating agent composition containing a polyimide resin with excellent adhesiveness and electrical properties, in detail, it can be used as a coating material for cords, cables, etc., a protective film for semiconductors, an insulating film,
This invention relates to a polyimide resin coating composition useful for paints and the like.

[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, 53
No. 3, 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 conduct 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, the film obtained by imidizing polyamic acid has the disadvantage that it does not have a 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 , 305, etc., but these solvent-soluble polyimide resins do not have sufficient coating strength and have a low glass transition point. The drawback is that it cannot withstand use at high temperatures.

The present inventors have already worked on JP-A-2-91.12 for another 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, in the present invention, in a polyimide resin coating agent composition containing at least a polyimide resin and an organic solvent, the polyimide resin has a 3.3' content.

4.4'-diphenylsulfonetetracarboxylic dianhydride and/or 4.4'-(hexafluoroisopropylidene)diphthalic dianhydride and the following general formula (I) (I) as a diamine component (however, the formula In the middle, X is 10-, -C(CH3)2- or C(
Aromatic diamine 50 represented by CFs)2-)
~99 mol% and the following general formula (I[)Rs Ri (wherein R1 and R2 are divalent organic groups, R3-R8
is an alkyl group, a phenyl group, or a substituted phenyl group, and n is an integer of 1 to 50) A polyimide precursor obtained by polycondensing a diamine component consisting of 1 to 50 mol% of a siloxane diamine This is a polyimide resin coating agent composition, which is an organic solvent-soluble polyimide resin obtained by imidizing.

The polyimide resin used in the present invention is synthesized from an aromatic carboxylic dianhydride and a diamine component. As such aromatic carboxylic dianhydride, 3.3°, 4.4
'-Diphenylsulfone tetracarboxylic dianhydride and/or 4,4'-(hexafluoroisopropylidene)
Diphthalic dianhydride is used.

In addition, the diamine component has the following general formula (I) (I) (wherein, X is 10--C(CH3)2- or C(C
R3) An aromatic diamine represented by (representing 2-) is used. Specifically, such aromatic diamines include 1,4-bis(4-aminophenoxy)benzene and 1,3-bis(4-aminophenoxy).
Benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4.4'-p-phenylenediisopropylidene)bisaniline, 4.4'-(m- 4. 4'-(1)-phenylene dihexafluoroisopropylidene) bisaniline, 4.
Examples include 4'-(m-phenylene dihexafluoroisopropylidene)bisaniline.

These may be used alone or in combination of two or more.

Furthermore, as the other diamine component, the following general formula (II
) 3Rs R2N-R1-E-31-Oh-81-R2-NH2R
4R, (n) (However, in the formula, R1 and R2 are divalent organic groups, R3-R6
is an alkyl group, a phenyl group, or a substituted phenyl group, and n is an integer of 1 to 50) is also used as an essential copolymerization component. Such siloxane diamines include H3CH3 H2N-(CH2)3÷5i-Oh-8i-(CH2)
, -NH2H3CH3 CH3CH3 H2N-(CH2)4+5i-(+h-si-(cH2
)4-Nu2CH3CH3 ph ph H2N-(CH2)3÷5i-Oh-3i-(CTo)
3-NH2ph ph ph ph and the like. These siloxane diamines have a weight average molecular weight of 200 to 5,000, preferably in the range of 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 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 dianhydride thing, 3.3', 4゜4
'-diphenyl ether tetracarboxylic dianhydride, 2
．． 3', 4.4'-diphenyl ethertetracarboxylic dianhydride, 2.3.6.7-naphthalenetetracarboxylic 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
．． 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, 3.4.9.10-perylenetetracarboxylic dianhydride, 4,4-bis(2,3-dicarboxyphenyl)diphenylmethanidianhydride things 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)toluene, bis(P-β-amino-tert-butylphenyl)ether, p-bis(2-methyl- 4-aminopentyl)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 an aromatic tetracarboxylic dianhydride and a 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, the reaction temperature is 0 to 100°C for 0.5 to 10 hours, and the obtained polyamic acid, which is a polyimide precursor, is imidized by dehydration and ring closure. can do. In addition, to control the degree of polymerization, phthalic anhydride, nadic anhydride, maleic anhydride, aniline,
It is also possible to add terminal capping agents such as benzoyl chloride. The polyimide resin thus obtained has a polymer concentration of 0.5 g/d in an organic solvent such as N-methyl-2-pyrrolidone! , the logarithmic viscosity measured at a temperature of 30°C is 0.1 to 5.0 dl/g1, preferably 0.
It is in the range of 2 to 3.0 dl/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. .

■Thermal imidization method in solution The polyimide precursor is heated to 100°C or higher in solution, preferably 1
Imidization is performed by heating to 30°C or higher. At this time, benzene, toluene, xylene, N
A solvent such as -cyclohexyl-2-pyrrolidone is preferably used, and a tertiary amine such as triethylamine, pyridine, N,N-dimethylaniline may be added as a reaction accelerator.

■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.

■ 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 resin thus obtained is N.

Since it completely dissolves in polar solvents such as N-methylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-cyclohexyl 2-pyrrolidone, and dimethyl sulfoxide, the polyimide resin after imidization can be used in these solvents. It can be used as a coating agent composition by dissolving it in , or it can be used as it is as a coating solvent without removing the solvent used in the polymerization reaction.

Various additives can be added to the polyimide resin coating composition of the present invention to impart properties depending on the purpose. Such additives include diethylene glycol dimethyl ether (diglyme), ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), and ethylene glycol monobutyl ether (butyl cellosolve).
Flowability improvers that improve the fluidity of the acetate derivatives thereof without impairing their solubility, abrasion resistance improvers such as graphite and molybdenum disulfide, glass fibers,
Fiber reinforcing agents such as carbon fiber and whiskers, flame retardant improvers such as magnesium carbonate, calcium carbonate, and antimony trioxide, electrical property improvers, oxidation stabilizers, silica, alumina,
Fillers such as titania, zirconia, and talc, pigments, and dyes can be mentioned.

〔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°-Diphenylsulfone tetracarboxylic 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 TPE-Q: 1.4-bis(4-aminophenoxy)benzene TPB-R: 1,3-bis(4-aminophenoxy)
Benzene B15A-P: 4.4'-(p-)x- diisopropylidene) bisaniline BisA-M: 4.4'-(m-phenylene diisopropylidene) bisaniline NMP: N-methyl-2-pyrrolidone DMAc:
N, N-dimethylacetamide DIG diethylene glycol dimethyl ether THF: Tetrahydrofuran In addition, for siloxane diamines, the following abbreviations are used depending on the average molecular weight.

FSX248: Average molecular weight 248 PSX480: z/ 480PSX740:
〃740 PSX1240:〃1240 Example 1 BPDA35゜8g in a 0.51 separable flask
(0.1 mol) was dispersed in DMAc200 vrl, and then 20.0 g (0.02
A solution of 7 mol) dissolved in 50 g of DIG was gradually added dropwise under water cooling, and after the completion of the dropwise addition, the reaction was allowed to proceed at 30° C. for 2 hours. Furthermore, TPE-Q21, 32 g (0,0
73 mol) was dissolved in 200 ynl of DMAc and gradually added dropwise to the above reaction solution, and after completion of the dropwise addition, the solution was stirred and reacted for 12 hours to obtain a polyamic acid solution.

Next, after adding 50% of toluene to this solution, 150% 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, 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.

(Effects 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, and has high heat resistance and excellent mechanical properties. It also has excellent adhesive properties and electrical properties, so 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 composition containing at least a polyimide resin and an organic solvent, the polyimide resin is 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride and/or 4,4'- (hexafluoroisopropylidene) diphthalic dianhydride;
As a diamine component, there are the following general formulas (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (However, in the formula, X represents -O-, -C(CH_3)_2- or -C(CF_3)_2- ) aromatic diamine represented by 50 to 99 mol% and the following general formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (However, in the formula, R_1 and R_2 are divalent organic groups, R_3
~R_6 is an alkyl group, a phenyl group, or a substituted phenyl group, and n is an integer of 1 to 50) A polyimide obtained by polycondensing a diamine component consisting of 1 to 50 mol% of a siloxane diamine A polyimide resin coating agent composition characterized in that it is an organic solvent-soluble polyimide resin obtained by imidizing a precursor. (2) The polyimide resin coating according to claim (1), wherein the organic solvent is at least one selected from the group consisting of ether solvents, amide solvents, phenol solvents, and dimethyl sulfoxide. agent composition.