JPH08253586A - Polyamideimide resin and vanish using the same - Google Patents

Abstract

PURPOSE: To obtain a polyamideimide resin which is lowly hygroscopic, soluble in a low boiling alcohol solvent and heat-resistant by using a polyamideimide resin containing a specific aliphatic dicarboxylic acid with a specific glass transition point. CONSTITUTION: This polyamideimide resin has a glass transition point of 120 deg.C or higher and contains an isophorone group and a 2-10C aliphatic dicarboxylic acid. Adipic acid and/or azelaic acid is desirable as an aliphatic dicarboxylic acid. A polyamideimide resin wherein a part of the aliphatic dicarboxylic acid is replaced by an aromatic polycarboxylic acid is more desirable. Further, a polyamideimide resin whose aromatic polycarboxylic acid is trimellitic acid and/or pyromellitic acid and in which 3-70mol% of the total acid component is copolymerized is even move desirable.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polyamide-imide resin. More specifically, it relates to a polyamide-imide resin having low hygroscopicity and solubility in an alcohol solvent having a low boiling point and having heat resistance, and a varnish containing the same.

[0002]

2. Description of the Related Art Polyamide-imide resins are widely used as fibers, films, molding materials and the like because of their excellent mechanical properties and heat resistance. However, currently known heat-resistant polyamide-imide resins are soluble only in highly hygroscopic amide solvents, high-boiling-point phenols, cresols, methylene chloride, etc., and therefore have stability over time during molding and drying. It was inferior in sex.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyamide-imide resin which has low hygroscopicity, is soluble in an alcohol solvent having a low boiling point, and has heat resistance, and a varnish using the same.

[0004]

In order to solve these problems, the inventors of the present invention have earnestly studied and, as a result, arrived at the present invention. That is, the present invention is a polyamide-imide resin having a glass transition temperature of 120 ° C. or higher and containing an isophorone residue and an aliphatic dicarboxylic acid having 2 to 10 carbon atoms and soluble in an alcohol solvent, The polyamide-imide resin, wherein the aliphatic dicarboxylic acid is adipic acid and / or azelaic acid, wherein the aliphatic dicarboxylic acid is partly replaced with an aromatic polycarboxylic acid. The polyamide-imide resin is an imide resin, the aromatic polycarboxylic acid is trimellitic acid and / or pyromellitic acid, and 3 to 70 mol% of all acid components are copolymerized. The present invention relates to the above-mentioned polyamide-imide resin. The present invention further relates to a polyamide-imide varnish obtained by dissolving the polyamide-imide resin in a polar solvent, and the polyamide-imide varnish wherein the polar solvent is an alcohol solvent.

The polyamideimide of the present invention can be produced by any method such as a melt polymerization method and a solution polymerization method. In the case of the solution polymerization method, it can be polymerized by a usual method such as an acid chloride method, a direct polymerization method, an isocyanate method, but in the industrially advantageous isocyanate method, one or more diisocyanates containing isophorone diisocyanate as an essential component are used. And dicarboxylic acid, and / or aromatic polycarboxylic acid 1
It can be obtained by reacting one or two or more species in an organic solvent at a temperature of 200 ° C. or lower.

The organic polar solvent used in the reaction includes ethers such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether, ketones such as cyclohexanone and methyl ethyl ketone, esters such as γ-butyrolactone and cellosolve acetate, and N-methyl-
Examples thereof include amides such as 2-pyrrolidone, dimethylimidazolidinone and dimethylacetamide, aromatic hydrocarbons such as xylene and toluene, and these are preferably used alone or as a mixture.

The reaction temperature is usually preferably 50 to 200 ° C., and the reaction is a catalyst for the reaction of isocyanate with an active hydrogen compound, for example, tertiary amines such as triethylamine, lutidine, picoline, undecene, triethylenediamine, sodium methylate, sodium. It may be carried out in the presence of an alkali metal such as ethylate, potassium butoxide, sodium fluoride or potassium fluoride, an alkaline earth metal compound, or a metal such as cobalt, titanium, tin or zinc, or a metalloid compound.

The characteristic feature of the polyamide-imide resin of the present invention is that it has a glass transition temperature of 120 ° C. or higher and is soluble in an alcohol solvent having a low boiling point. This is achieved by using an isophorone residue and one or more aliphatic dicarboxylic acids having 2 to 10 carbon atoms as essential components. In particular, the aliphatic dicarboxylic acid is adipic acid and / or azelaic acid. Good results are obtained when the aromatic polycarboxylic acid is trimellitic anhydride or pyromellitic anhydride.

In obtaining the polyamide-imide resin of the present invention, it is necessary to use an aliphatic dicarboxylic acid having 2 to 10 carbon atoms as an acid component, but other aliphatic dicarboxylic acids, undecanedioic acid, dodecane are required. One kind or a mixture of two or more kinds such as diacid, tridecanedioic acid and tetradecanedioic acid may be copolymerized. Further, an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid may be copolymerized.

As the aromatic polycarboxylic acid, there are tricarboxylic acids such as trimellitic acid and naphthalene-1,2,4-tricarboxylic acid, and their anhydrides.

Or / and pyromellitic acid, benzophenone-3,3 ', 4,4'-tetracarboxylic acid, diphenyl ether-3,3', 4,4'-tetracarboxylic acid,
Benzene-1,2,3,4-tetracarboxylic acid, biphenyl-3,3 ', 4,4'-tetracarboxylic acid, biphenyl-2,2', 3,3'-tetracarboxylic acid, naphthalene-2, 3,6,7-Tetracarboxylic acid, naphthalene-1,2,4,5-tetracarboxylic acid, naphthalene-
1,4,5,8-Tetracarboxylic acid, decahydronaphthalene-1,4,5,8-tetracarboxylic acid, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene- 1,2,5,6-tetracarboxylic acid, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid, 2,3,6,7-Tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid, Phenanthrene-1,3,9,10-tetracarboxylic acid, Berylene-3,4,9,10-tetracarboxylic acid Acid, bis (2,3
-Dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) methane, 1,1-bis (2,3-dicarboxyphenyl) ethane, 1,1-bis (3,4-
Dicarboxyphenyl) ethane, 2,2-bis (2,3
-Tetracarboxy such as dicarboxyphenyl) propane, 2,3-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) ether Although it is necessary to use one or more of acids and their anhydrides, isophthalic acid, 5-tert
-Butyl-1,3-benzenedicarboxylic acid, terephthalic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylmethane-2,4'-dicarboxylic acid, diphenylmethane-3,4'-dicarboxylic acid, diphenylmethane-
3,3'-dicarboxylic acid, 1,2-diphenylethane-
4,4'-dicarboxylic acid, 1,2-diphenylethane-
2,4'-dicarboxylic acid, 1,2-diphenylethane-
3,4'-dicarboxylic acid, 1,2-diphenylethane-
3,3′-dicarboxylic acid, 2,2-bis (4-carboxyphenyl) propane, 2,2-bis (3-carboxyphenyl) propane, 2- (2-carboxyphenyl)
-2- (4-carboxyphenyl) propane, 2- (3
-Carboxyphenyl) -2- (4-carboxyphenyl) propane, diphenyl ether-4,4-dicarboxylic acid, diphenyl ether-2,4-dicarboxylic acid, diphenyl ether-3,4-dicarboxylic acid, diphenyl ether-3,3-dicarboxylic acid , Diphenyl sulfide-4,4-dicarboxylic acid, diphenyl sulfide-
2,4-dicarboxylic acid, diphenyl sulfide-3,4
-Dicarboxylic acid, diphenyl sulfide-3,3-dicarboxylic acid, diphenyl sulfone-4,4-dicarboxylic acid, diphenyl sulfone-2,4-dicarboxylic acid, diphenyl sulfone-3,4-dicarboxylic acid, diphenyl sulfone-3,3 -Dicarboxylic acid, benzophenone-4,
4-dicarboxylic acid, benzophenone-2,4-dicarboxylic acid, benzophenone-3,4-dicarboxylic acid, benzophenone-3,3-dicarboxylic acid, 1,1,3-trimethyl-5-carboxy-3- (p-carboxy Aroma such as phenyl) indane, pyridine-2,6-dicarboxylic acid, bis [(4-carboxy) phthalimide] -4,4′-diphenyl ether, bis [(4-carboxy) phthalimide] -α, α′-meta-xylene A group dicarboxylic acid may be copolymerized.

These aromatic polycarboxylic acids are used within the range in which the effects of the present invention can be achieved, but usually 3 to 70 mol%, preferably 5 to 30 mol% of the total acid components.
Used in the range of. The ratio of aromatic polycarboxylic acid is 3
If it is less than mol%, the glass transition temperature is lowered to 70 mol.
When it is more than%, it becomes difficult to dissolve in a polar solvent such as alcohol.

As the amine component used in the present invention, it is necessary to use isophoronediamine. One or two of the following diamines or diisocyanates are used.
Copolymerization of more than one species is also possible.

Specifically, hexamethylenediamine, tetramethylenediamine, 4,4-diaminocyclohexyl, 4,4-diaminodicyclohexylmethane, 1,3
-Bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 4,4-diaminodiphenylmethane, 3,3-diaminodiphenylmethane, 2,4-dimethylmetaphenylenediamine, 5-nitrometaphenylenediamine, 5-
Chlorometaphenylenediamine, 4,4-diaminodiphenylhexafluoropropane, 3,3-diaminodiphenylhexafluoropropane, 4,4-diaminodiphenylsulfone, 3,3-diaminodiphenylsulfone, 4,4-diaminodiphenylsulfide, 3 , 3
-Diaminodiphenyl sulfide, 4,4-diaminobenzophenone, 3,3-diaminobenzophenone, 3,
4-diaminobiphenyl, 3,3-diaminobiphenyl, isopropylidenedianiline, 3,3-diaminodiphenylpropane, 2,4-tolylenediamine, 3,3
-Diaminobenzanilide, 4,4-diaminobenzanilide, o-tolidine, 1,4-naphthalenediamine,
1,5-naphthalenediamine, 2,6-naphthalenediamine, 2,7-naphthalenediamine, 2,2-bis (4
-Aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4
-Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4- [1,3-phenylenebis (1-methylethylidene)] bisaniline,
4,4- [1,4-phenylenebis (1-methylethylidene)] bisaniline, 3,3- [1,3-phenylenebis (1-methylethylidene)] bisaniline, 2,2
-Bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl]
Propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, Bis [4- (3-aminophenoxy) phenyl] sulfone,
4,4-bis (3-aminophenoxy) biphenyl,
4,4-bis (4-aminophenoxy) biphenyl and the like can be mentioned.

The diamine or diisocyanate which may be copolymerized is used in a range not deteriorating the characteristics of the polyamideimide of the present invention, but usually 70% of all diamine components.
It is at most mol%, preferably at most 40 mol%.

The optimum value of the molecular weight of the polyamide-imide of the present invention depends on each composition and use, but N-methyl-2
-In pyrrolidone, the logarithmic viscosity value by Ubbelohde viscosity tube at 30 ° C is 0.1 dl / g or more, preferably 0.2 dl
/ G or more.

When the polyamideimide resin of the present invention is used as a varnish, it is dissolved in a solvent such as dimethylformamide, dimethylacetamide, phenol, cresol, methylene chloride, benzyl alcohol, etc., which is a solvent for ordinary polyamideimide having heat resistance. In addition, it is also soluble in alcohol-based organic solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, and xylenol, which cannot be dissolved by conventional heat-resistant polyamide-imide polymers. Further, the above alcohol solvent and tetrahydrofuran, diglyme, ether organic solvents such as dioxane,
It is also soluble in a mixed solvent with a ketone-based organic solvent such as cyclohexanone, cyclopentanone and methyl isobutyl ketone, an ester-based organic solvent such as ethyl acetate and methyl acetate, an aromatic hydrocarbon-based organic solvent such as toluene.

The polyamide-imide resin of the present invention can be molded by a conventionally known method such as solution casting, dry spinning, wet spinning, gel spinning, melt molding and injection molding. In particular, in solution casting such as solution casting and dry spinning, the solvent used has a low boiling point and a low hygroscopic property.
It is easy to handle, and the physical properties of the resulting molded products are far superior to those of conventional molded products.

The form of the molded article is not particularly limited, and examples include molded articles such as films, fibers, hollow fibers, pipes and bottles. There is no particular limitation on the use, but for automobiles,
Chemical plants, aviation / space, machinery, electrical / electronic components,
It can also be used as a material.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 The following polymerization components were charged in a reaction vessel and stirred with stirring at 150
The temperature was raised to ° C, and then the mixture was stirred for about 6 hours. Polymerization component Azelaic acid 0.9 mol Pyromellitic anhydride 0.1 mol Isophorone diisocyanate 0.5 mol 4,4-Dicyclohexyl diisocyanate 0.5 mol Potassium fluoride 0.02 mol γ-butyrolactone 350 ml Next, this polyamideimide The polymer solution was diluted with N-methyl-2-pyrrolidone and reprecipitated with water to obtain a polyamideimide powder.

The above polyamideimide powder was dissolved in a mixed solvent of methanol and toluene so that the solid content concentration was 30% by weight. The ratio of methanol and toluene was 50/50 in volume%. This solution was applied onto a releasable polyester film so that the thickness after drying would be 30 μm,
After drying at 100 ° C. for 5 minutes, it was peeled from the release film. Table 1 shows measured values of various properties of the polyamide-imide film thus obtained.

Example 2 Of the polymerization components used in Example 1, trimellitic anhydride was used in place of pyromellitic anhydride,
Polyamideimide and a polyamideimide film were obtained by the same procedure as in Example 1. Various properties of the obtained polyamideimide film were measured in the same manner as in Example 1. The results are shown in Table 1.

Example 3 Of the polymerization components used in Example 2, isophorone diamine was used instead of isophorone diisocyanate, 4,
4, instead of 4-dicyclohexyl diisocyanate
Using 4-dicyclohexyldiamine, the mixture was heated to 260 ° C., melted and stirred for 3 hours. The obtained polyamide-imide was dissolved, coated and peeled off in the same manner as in Example 1 to obtain a polyamide-imide film. Various properties of the obtained polyamideimide film were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 Among the polymerization components used in Example 1, undecanedioic acid was used instead of azelaic acid to obtain a polyamideimide and a polyamideimide film in the same procedure as in Example 1. Various properties of the obtained polyamideimide film were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 Polyamideimide was obtained by the same procedure as in Example 1 except that azelaic acid was 0.2 mol and pyromellitic acid was 0.8 mol among the polymerization components used in Example 1. .
The obtained polyamide-imide did not dissolve in methanol.

[0027]

[Table 1]

The measuring method of each characteristic in the table is shown below. Logarithmic viscosity: 0.5 g / in N-methyl-2-pyrrolidone
It was measured at a concentration of dl at 30 ° C. using an Ubbelohde viscosity tube. Tg (° C): Measured by the TMA tensile load method. Load: 1 g, sample size: 5 × 20 mm, temperature rising rate: 10 ° C./min Tensile strength, tensile elongation, tensile modulus: JIS-C-231
8 was measured.

[0029]

INDUSTRIAL APPLICABILITY The polyamide-imide of the present invention is not only soluble in amide-based polar solvents, phenol-based solvents, etc., which are conventionally known solvents for amide-imide-based polymers having heat resistance, but also cyclohexanone, tetrahydrofuran, methanol. It is also soluble in solvents with low hygroscopicity and low boiling points, such as ethanol, isopropyl alcohol and the like. Therefore, it is excellent in solution moldability such as stability with time during molding and drying property.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomoharu Kurita 2-1-1 Katata, Otsu City, Shiga Prefecture Toyobo Co., Ltd.

Claims (6)

[Claims] 1. A polyamide-imide resin having a glass transition temperature of 120 ° C. or higher and containing an isophorone residue and an aliphatic dicarboxylic acid having 2 to 10 carbon atoms and soluble in an alcohol solvent. 2. The aliphatic dicarboxylic acid is adipic acid or /
The polyamide-imide resin according to claim 1, which is azelaic acid. 3. The polyamideimide resin according to claim 1, which is a polyamideimide resin in which a part of the aliphatic dicarboxylic acid is replaced with an aromatic polycarboxylic acid. 4. The aromatic polyvalent carboxylic acid is trimellitic acid and / or pyromellitic acid, and 3 to 3 of all acid components are used.
70 mol% was copolymerized.
The polyamide-imide resin according to any one of 3 above. 5. A polyamideimide varnish obtained by dissolving the polyamideimide resin according to claim 1 in a polar solvent. 6. The polyamide-imide varnish according to claim 5, wherein the polar solvent is an alcohol solvent.