JPH1067934A - Water-soluble polyimide-imide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject component useful for a plastic film high in solubility in water free from environmental pollution and low in processing cost, containing a polyimide resin having a specific logarithmic viscosity and a prescribed acid value. SOLUTION: This composition comprises (B) a polyimide resin soluble in a basic aqueous solution. The component B has >=0.1dL/g intrinsic viscosity and >=30 equivalent/10<6> g acid value. The component B contains a metal inonic group, preferably 5-sulfoisophthaloyl group in the ratio of the group to an acid component or amine component constituting the component B of >=0.1mol%. The component A is at least a kind of aqueous solutions of ammonia and a water-soluble amine having <=200 deg.C boiling point. The objective composition is preferably obtained by polymerizing the component B in a polar organic solvent, mixing the prepared reaction solution with water to coagulate the component B, desolvating and stirring the prepared component B in the component A under heating.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition containing a water-soluble polyamideimide resin and capable of solution processing.

[0002]

2. Description of the Related Art Polyamide imide resin is a resin which is excellent in heat resistance, chemical resistance, abrasion resistance and the like and can be injection-molded. In addition, an amide resin such as N-methyl-2-pyrrolidone is used. Since it is soluble in solvents, it has the property that solution processing is possible. Therefore, it has been used for molding materials, heat-resistant insulating paints, and the like.

[0003] However, conventional aromatic polyamide-imide resins are insoluble in solvents other than amide-based resins and have disadvantages such as that the resin itself is colored, hard, brittle, and the like. , Molding materials and the like.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems, and an object of the present invention is to provide a polyamideimide having a high solubility in a general-purpose solvent such as water. It is an object of the present invention to provide a composition containing a polyamide-imide resin having properties inherent to the resin, that is, properties excellent in heat resistance and chemical resistance. Another object of the present invention is to provide a polyamideimide resin composition which can be easily processed at low cost and can be coated on a metal without causing environmental pollution due to the above properties. Still another object of the present invention is to provide a method for preparing a polyamideimide resin-containing basic aqueous solution containing the above polyamideimide resin and useful for solution processing.

[0005]

Means for Solving the Problems As a result of diligent studies on the above problems, the present inventors have developed a composition containing a polyamideimide resin that can be dissolved in a basic aqueous solution.

The composition containing the water-soluble polyamide-imide resin of the present invention has a logarithmic viscosity of 0.1 dl / g or more and an acid value of 30 equivalent / 10 ⁶ in the polyamide-imide resin contained therein.
g or more, and 0.1% by mole of an acid component or an amine component constituting the resin in the polyamideimide resin.
In the preferred embodiment, the metal ionic group is contained in the above ratio, whereby the object is achieved.
-A sulfoisophthaloyl group.

In a preferred embodiment, the basic aqueous solution is at least one of an aqueous solution of ammonia and a water-soluble amine having a boiling point of 200 ° C. or lower.

The method for producing a basic aqueous solution containing a polyamide-imide resin according to the present invention comprises a step of preparing the above-mentioned polyamide-imide resin by a polymerization reaction in a polar organic solvent, and a step of mixing the reaction solution containing the polyamide-imide resin with water. And coagulating the polyamide-imide resin, and then removing the solvent, and heating and stirring the obtained polyamide-imide resin in a basic aqueous solution.

[0009]

DETAILED DESCRIPTION OF THE INVENTION As described above, the polyamideimide resin contained in the composition of the present invention has a logarithmic viscosity of 0.1 dl / g or more and an acid value of 30 equivalents / 10 ⁶ g or more, The polyamide-imide resin contains a metal ionic group in an amount of 0.1 mol% or more of the acid component or the amine component constituting the resin. Such a polyamide-imide resin is obtained by copolymerizing an acid component, an amine component, and a compound containing a metal ionic group.

The acid component is not particularly limited, but basically trimellitic acid or its anhydride (which may be in the form of acid chloride) because of its low cost and excellent reactivity. And a part thereof can be replaced with a polycarboxylic acid other than trimellitic acid or an anhydride thereof (which may be in the form of an acid chloride).

As the polyvalent carboxylic acid, dicarboxylic acid, tricarboxylic acid or tetracarboxylic acid may be used, and these may be any of aliphatic, alicyclic and aromatic.

The aliphatic dicarboxylic acids which can be used as polycarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecane Diacids, tridecandioic acids, and their acid chlorides are mentioned, and alicyclic dicarboxylic acids include cyclohexanedicarboxylic acid and its acid chlorides. Among them, cyclohexanedicarboxylic acid is particularly preferred from the viewpoint of high polymerizability and excellent transparency, heat resistance and chemical resistance of the obtained polyamideimide resin.

The aromatic dicarboxylic acids which can be used as polycarboxylic acids include 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, diphenylethane-2,4-dicarboxylic acid, diphenylethane-3,4-dicarboxylic acid, diphenylethane-3,3′-dicarboxylic acid, 2,2′-bis- (4-carboxyphenyl) propane, -(2-carboxyphenyl) -2- (4-carboxyphenyl)
Propane, 2- (3-carboxyphenyl) -2- (4
-Carboxyphenyl) propane, diphenylether-4,4'-dicarboxylic acid, diphenylether-2,
4-dicarboxylic acid, diphenylether-3,4-dicarboxylic acid, diphenylether-3,3'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, diphenylsulfone-2,4-dicarboxylic acid, diphenylsulfone-3, 4-dicarboxylic acid, diphenylsulfone-3,3'-dicarboxylic acid, benzophenone-4,4 '
-Dicarboxylic acid, benzophenone-3,3'-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, naphthalenedicarboxylic acid, bis-[(4-carboxy) phthalimide]
-4,4'-diphenyl ether, bis-[(4-carboxy) phthalimide]-[alpha], [alpha] '-metaxylene and acid chlorides thereof. In particular, isophthalic acid and terephthalic acid are preferred in that they are inexpensive and excellent in polymerizability.

The tricarboxylic acids that can be used as polycarboxylic acids include butane-1,2,4-tricarboxylic acid, naphthalene-1,2,4-tricarboxylic acid, and their acid chlorides.

The tetracarboxylic acids which can be used as polycarboxylic acids include butane-1,2,3,4-tetracarboxylic acid, pyromellitic acid, benzophenone-3,3 ',
4,4'-tetracarboxylic acid, diphenyl ether-
3,3 ′, 4,4′-tetracarboxylic acid, diphenyl ether-3,3 ′, 4,4′-tetracarboxylic acid, biphenyl-3,3 ′, 4,4′-tetracarboxylic acid, naphthalene-2, 3,6,7-tetracarboxylic acid, naphthalene-1,2,4,5-tetracarboxylic acid, naphthalene-
Examples include 1,4,5,8-tetracarboxylic acid and their acid chlorides.

As the anhydride of the polycarboxylic acid, any acid anhydride corresponding to the polycarboxylic acid can be used, and the following acid anhydrides are preferable: pyromellitic anhydride, Benzophenonetetracarboxylic anhydride, 3,
3 ', 4,4'-diphenylsulfonetetracarboxylic anhydride, 3,3', 4,4'-diphenyltetracarboxylic anhydride, 4,4'-oxydiphthalic anhydride, trimellitic anhydride, ethylene Glycol bisanhydrotrimellitate, propylene glycol bisanhydrotrimellitate, 1,4-butanediol bisanhydrotrimellitate, hexamethylene glycol bisanhydrotrimellitate, polyethylene glycol bisanhydrotrimellitate, Such as polypropylene glycol bisanhydrotrimellitate. Of these,
Ethylene glycol bisanhydrotrimellitate
It is preferable in terms of excellent polymerizability and low cost, and excellent flexibility and adhesion of the obtained polyamideimide resin.

The above-mentioned acid components other than trimellitic anhydride may be used alone or in combination with a part of trimellitic anhydride.

The amine component used in the present invention includes:
Typically, a diamine is used, and a diisocyanate in which the amino group of the diamine is substituted with -N = C = O can also be used. As used herein, the term “amine component” refers to at least one of a diamine and a diisocyanate.

The diamine is not particularly limited, but any of aromatic diamine, aliphatic diamine and alicyclic diamine can be used.

Examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, oxydianiline, methylenediamine, hexafluoroisopropylidenediamine, diamino-m-xylylene, diamino-p
-Xylylene, 1,4-naphthalenediamine, 1,5-
Naphthalenediamine, 2,6-naphthalenediamine,
2,7-naphthalenediamine, 2,2'-bis- (4-
Aminophenyl) propane, 2,2′-bis- (4-aminophenyl) hexafluoropropane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylether, 3,3′-diaminodiphenylsulfone, 3 , 3'-Diaminodiphenyl ether, 3,4-
Diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4-diaminodiphenyl ether, isopropylidene dianiline, 3,3'-diaminobenzophenone, o-tolidine, 2,4-tolylenediamine, 1,3
-Bis- (3-aminophenoxy) benzene, 1,4-
Bis- (4-aminophenoxy) benzene, 1,3-bis- (4-aminophenoxy) benzene, 2,2-bis- [4- (4-aminophenoxy) phenyl] propane,
Bis- [4- (4-aminophenoxy) phenyl] sulfone, bis- [4- (3-aminophenoxy) phenyl] sulfone, 4,4′-bis- (4-aminophenoxy) biphenyl, 2,2′- Bis- [4- (4-aminophenoxy) phenyl] hexafluoropropane, 4,4′-
Examples thereof include diaminodiphenyl sulfide and 3,3′-diaminodiphenyl sulfide.

Examples of the aliphatic diamine include ethylene diamine, propylene diamine, tetramethylene diamine, and hexamethylene diamine.

Examples of the alicyclic diamine include isophorone diamine and 4,4'-diaminocyclohexylmethane.

The diisocyanates include all diisocyanates derived from these above-mentioned diamines.

Among the above amine components, 4,4'-diaminodiphenylmethane and the corresponding 4,4'-diphenylmethane diisocyanate are particularly preferable because of their excellent reactivity and low cost.

The above amine components can be used alone or in combination.

Examples of compounds containing a metal ionic group include dicarboxylic acids, diisocyanates and phosphorus compounds having an anionic group; dicarboxylic acids having a cationic group; and polybasic acid anhydrides.

Dicarboxylic acids having an anionic group include monosodium trimellitate, monopotassium trimesate, sodium 5-sulfoisophthalate, 5-sodium carboxytrimellitic anhydride, and 2-carboxyethylphosphonic acid. Including monopotassium salts. The diisocyanate having an anionic group includes sodium sulfonic acid salt adduct to diphenylmethane 4,4′-diisocyanate, and the like. Examples of the phosphorus compound having an anionic group include the compounds shown below. :

[0028]

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Compounds having a cationic group include the following compounds:

[0030]

Embedded image

Among them, 5-isosulfoisophthalate is excellent in terms of excellent polymerizability, high water solubility of the obtained polyamideimide resin, and low cost of preparing the polyamideimide resin. Sodium acid is particularly preferred.

The compound containing a metal ionic group is
They can be used alone or in combination.

The above-mentioned acid component and amine component are generally mixed and copolymerized in equimolar amounts, but if necessary, one component may be slightly increased or decreased with respect to the other component. In the preparation of the polyamide-imide resin of the present invention,
In order to slightly increase the acid value, it is preferable to carry out polymerization by mixing an acid component in a slightly excessive amount. This is because the water solubility of the polyamide-imide resin is considered to be affected by a carboxyl group derived from an acid component, in addition to the effect resulting from the inclusion of the compound having a metal ionic group in the resin component. .

The compound having a metal ionic group used for imparting water solubility to the polyamideimide resin is 0.1 mol% or more of the total acid component or amine component (in terms of carboxyl group or amino group (isocyanate group)). Is preferably contained at a ratio of (d). In other words,
A compound having an anionic group is used as a part of an acid component, and a compound having a cationic group is used as a part of an amine component. A compound having an anionic group and a compound having a cationic group may be used as a mixture. When used as a mixture, the sum of the ratio of the compound having an anionic group to the entire acid component and the ratio of the compound having a cationic group to the entire amine component may be 0.1 mol% or more. . It is contained in a proportion of 0.1 mol% or more of all the components. The content of the compound having a metal ionic group with respect to the entirety of these components is more preferably 0.5 to 20 mol% from the viewpoint of excellent water solubility and polymerizability, and particularly preferably,
1.0 to 10 mol%. When the content of the acid component or the amine component is 0.1 mol% or less, the obtained polyamideimide resin has poor water solubility.

As the solvent used for preparing the polyamide-imide resin of the present invention, an amide solvent (for example,
N-methyl-2-pyrrolidone, dimethylacetamide,
Dimethylformamide, dimethylimidazolidinone),
Sulfur solvents (eg, dimethyl sulfoxide, sulfolane), nitro solvents (eg, nitromethane, nitroethane), ether solvents (eg, diglyme, tetrahydrofuran, dioxane), ketone solvents (eg,
Cyclohexanone, methyl ethyl ketone), nitrile solvents (eg, acetonitrile, propionitrile),
And a solvent having a relatively high dielectric constant (eg, γ-butyrolactone, tetramethylurea, ethylene carbonate)
Among them, N-methyl-2-pyrrolidone, dimethylimidazolidinone, and γ-butyrolactone are particularly preferred in that a resin having a high degree of polymerization can be obtained. These solvents may be used alone or in combination, and may be used in combination with a solvent having a relatively low dielectric constant (eg, xylene, toluene) as compared with the above-mentioned solvents.

The polyamideimide resin can be obtained by reacting the above-mentioned acid component and amine component, and a compound having a metal ionic group by a conventional method, for example, an acid chloride method and an isocyanate method. That is, a desired polyamideimide resin can be easily produced by dissolving an acid component, an amine component, and a compound having a metal ionic group in a polymerization solvent and then heating and stirring. In particular, when diisocyanate is used as the amine component, it is preferable to react in the presence of a catalyst in order to promote the reaction between diisocyanate and active hydrogen. Examples of the catalyst include amines (eg, triethylamine, lutidine, picoline, triethylenediamine), alkali metal and alkaline earth metal compounds (eg, lithium methoxide, sodium methoxide, potassium butoxide, potassium fluoride, fluoride) Sodium) or metal and semi-metallic catalysts (eg, cobalt, titanium, tin, zinc) can be used. Among these catalysts, potassium fluoride is particularly preferred. The copolymerization reaction is usually preferably performed at
220 ° C. temperature range, more preferably 80 ° C. to 220 ° C.
It is performed in a temperature range of ° C.

As described above, a polyamideimide resin is obtained. The logarithmic viscosity of this resin is required to be 0.1 dl / g or more, preferably 0.2 dl / g or more from the viewpoint of improving toughness, flexibility and the like.
This is because if the logarithmic viscosity is 0.1 dl / g or less, the abrasion resistance and heat resistance of the resin are reduced and the resin becomes brittle. Further, the acid value of this polyamide-imide resin is 30
And the equivalent / 10 ⁶ g or more, preferably, 50 equivalents / 1
From 0 ⁶ g is the 3000 equivalent / 10 ⁵ g. When the acid value is 30 equivalents / 10 ⁶ g or less, the solubility in water is low, and when a dispersion is applied, a uniform coating film cannot be formed.

Next, a preferred method for preparing a composition containing a desired water-soluble polyamide-imide resin will be described. The polyamide-imide resin is prepared by a polymerization reaction in an organic solvent, and after the polymerization reaction is stopped, a polymerization solution containing a desired polyamide-imide resin is mixed with water to solidify the polyamide-imide resin, and the solvent is removed. Is dissolved in a basic aqueous solution.
The method for removing the solvent is not particularly limited, and examples thereof include a method known to those skilled in the art, such as a method of washing with water, a dry spinning method, and a wet spinning method. In particular, the wet spinning method is preferable, and the method includes a non-solvent (preferably, water) that is miscible with the polymerization solvent.
The polymerization solution containing the polyamideimide resin obtained in the coagulation bath containing is extruded from a nozzle to coagulate and wash the polyamideimide resin. When dissolving the obtained polyamideimide resin in a basic aqueous solution, furthermore, a high-speed impeller, a side mill,
Dispersers such as ball mills can also be used.

The basic aqueous solution for dissolving the desired water-soluble polyamideimide resin is not particularly limited, but may be an inorganic base (eg, sodium hydroxide, potassium hydroxide,
Aqueous solutions of sodium carbonate, potassium carbonate) and amines (primary, secondary, tertiary amines). Particularly preferred are aqueous ammonia and an aqueous solution of a tertiary amine having a boiling point of 200 ° C. or lower (eg, trimethylamine and triethylamine, and preferably triethylamine) because of its excellent water solubility. The polyamideimide resin obtained as described above is dissolved in such a basic aqueous solution. Upon dissolution, it is preferable to heat and stir the polyamideimide resin in a basic aqueous solution as necessary as described above.

As described above, according to the present invention, it is possible to impart water solubility without impairing the inherent properties of the polyamideimide resin, such as heat resistance and chemical resistance. This makes it possible to process the resin in an aqueous solution and to reduce the chance of unnecessary use of an organic solvent, so that it is possible to produce a plastic film or metal coating material with low environmental pollution and low cost.

[0041]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. The properties of the polyamideimide resin in the examples were measured by the following methods.

Logarithmic viscosity: 0.5 g of polyamide-imide resin
Is dissolved in 100 ml of N-methyl-2-pyrrolidone,
The logarithmic viscosity was determined by measuring with an Ubbelohde viscosity tube. Acid value: Measured by potentiometric titration to determine the acid value.

Example 1 Trimellitic anhydride (acid component), sodium 5-sulfoisophthalate were placed in a reaction vessel.
(Compound containing a metal ionic group; acid component) and diphenylmethane diisocyanate (amine component) in the molar ratio shown in Table 1 and N-methyl-2 so that the solid concentration becomes 30% by weight. -Charged with pyrrolidone. The amount of sodium 5-sulfoisophthalate is shown in mol% based on the total acid component. The mixture was heated to 180 ° C. and reacted for 5 hours, and then cooled to stop the reaction. The resulting polymerization solution was then added to stirring water and the resulting solid was washed with water and dried.
The logarithmic viscosity and the acid value of the obtained polyamideimide resin were determined as described above. Table 1 shows the evaluation results.

Next, an aqueous ammonium hydroxide solution (80 g) having an equivalent of 10 times the acid value was added to the obtained dried polyamideimide resin (20 g) and dissolved at 60 ° C. for about 2 hours. Table 1 shows the evaluation results.

Here, Δ in Table 1 indicates that the resin was completely dissolved, and X indicates that the resin was not completely dissolved.

Example 2 5 mol% based on the total acid component
A polyamide-imide resin was obtained in the same manner as in Example 1 except that sodium 5-sulfoisophthalate was used. Table 1 shows the evaluation results of the obtained resins.

Example 3 A polyamideimide resin was obtained in the same manner as in Example 1 except that 10 mol% of sodium 5-sulfoisophthalate was used based on the entire acid component. Table 1 shows the evaluation results of the obtained resins.

Example 4 A polyamideimide resin was obtained in the same manner as in Example 1, except that 30 mol% of sodium 5-sulfoisophthalate was used based on the entire acid component. Table 1 shows the evaluation results of the obtained resins.

<Example 5> 10 mol% of sodium 5-sulfoisophthalate was used based on the whole acid component,
The number of moles of the acid component / the number of moles of the diisocyanate component is set to 1.
A polyamide-imide resin was obtained in the same manner as in Example 1 except that the value was 10. Table 1 shows the evaluation results of the obtained resins.

Example 6 10 mol% of sodium 5-sulfoisophthalate was used based on the whole acid component.
The number of moles of the acid component / the number of moles of the diisocyanate component is set to 1.
A polyamideimide resin was obtained in the same manner as in Example 1 except that the resin composition was changed to 05. Table 1 shows the evaluation results of the obtained resins.

<Example 7> 10 mol% of sodium 5-sulfoisophthalate was used based on the whole acid component,
The number of moles of the acid component / the number of moles of the diisocyanate component is set to 1.
A polyamideimide resin was obtained in the same manner as in Example 1 except that the value was changed to 00. Table 1 shows the evaluation results of the obtained resins.

Comparative Example 1 The number of moles of the acid component / the number of moles of the diisocyanate component was 1.05, and sodium 5-sulfoisophthalate, which is a compound containing a metal ionic group, was not copolymerized. A polyamide-imide resin was obtained in the same manner as in Example 1 except for the above. Table 1 shows the evaluation results of the obtained resins.

Comparative Example 2 The number of moles of the acid component / the number of moles of the diisocyanate component was set to 0.97, and sodium 5-sulfoisophthalate, a compound containing a metal ionic group, was not copolymerized. A polyamide-imide resin was obtained in the same manner as in Example 1 except for the above. Table 1 shows the evaluation results of the obtained resins.

[0054]

[Table 1]

As shown in Table 1, the polyamide imide resins containing metal ionic groups (Examples 1 to 7) were completely dissolved in the aqueous ammonium hydroxide solution and had high water solubility. In comparison, the polyamideimide resin containing no compound containing a metal ionic group (Comparative Examples 1 and 2) was not completely dissolved in the aqueous ammonium hydroxide solution and had low water solubility.

Furthermore, in the water-soluble polyamide-imide resin of the present invention, it was confirmed that the inherent properties of the polyamide resin, such as heat resistance and chemical resistance, were not impaired. Confirmed by

[0057]

According to the present invention, there is provided a composition containing a polyamideimide resin having high solubility in water and having excellent properties of the original polyamideimide resin such as heat resistance and chemical resistance. Is done. Accordingly, a plastic film, a metal coating material, and the like that are free from environmental pollution and low in processing cost can be provided.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Hiroki Yamaguchi 2-1-1 Katata, Otsu City, Shiga Prefecture Toyobo Co., Ltd. Research Laboratory

Claims (4)

[Claims] 1. A composition containing a polyamideimide resin that can be dissolved in a basic aqueous solution, wherein the polyamideimide resin has a logarithmic viscosity of 0.1 dl / g or more and an acid value of 30 equivalents / 10 ⁶ g or more. And a composition wherein the polyamide-imide resin contains a metal ionic group in a proportion of 0.1 mol% or more of an acid component or an amine component constituting the resin. 2. The composition according to claim 1, wherein the metal ionic group is a 5-sulfoisophthaloyl group. 3. The composition according to claim 1, wherein the basic aqueous solution is at least one of an aqueous solution of ammonia and a water-soluble amine having a boiling point of 200 ° C. or lower. 4. A method for producing a basic aqueous solution containing the polyamideimide resin according to claim 1, wherein the polyamideimide resin is prepared by a polymerization reaction in a polar organic solvent. Mixing the reaction liquid containing the polyamide-imide resin with water to coagulate the polyamide-imide resin, then removing the solvent, and heating and stirring the obtained polyamide-imide resin in a basic aqueous solution, Production method.