JPH11130832A - Siloxane-containing polyamide imide, its production and varnish containing the polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polyamide imide soluble in solvents and having high molecular weight and excellent film-forming property by reacting a specific diisocyanate compound with a mixture containing a specific diimide carboxylic acid produced by reacting trimellitic anhydride with a mixture of a specific diamine and a siloxane diamine. SOLUTION: The objective polyamide imide can be produced by reacting (A) a mixture of (i) a diamine having >=3 aromatic rings and (ii) a siloxane diamine with (B) trimellitic anhydride and reacting the obtained mixture containing a diimide dicarboxylic acid of formula I [R1 is a group of formula II (X is a group of formula III)] and the formula IV [R2 is a group of formula V (R3 and R4 are each a bivalent organic group; R5 to R8 are each an alkyl or the like; (n) is 1-50)] with (C) an aliphatic or alicyclic aliphatic diisocyanate compound of the formula, OCN-R9 -NCO [R9 is a bivalent (substituted)aliphatic group or the like].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a mixture of a diimidedicarboxylic acid obtained by reacting a mixture of a diamine and a siloxanediamine having three or more aromatic rings with trimellitic anhydride and an aliphatic or cycloaliphatic aliphatic compound. The present invention relates to a siloxane-containing polyamideimide obtained by reacting with diisocyanate, a method for producing the same, and a varnish containing the same.

[0002]

2. Description of the Related Art Polyamide imides are usually synthesized by an isocyanate method by the reaction of trimellitic anhydride and an aromatic diisocyanate, or by an acid chloride method by a reaction of an aromatic diamine and trimellitic acid chloride. I have. In the isocyanate method, the types of aromatic diisocyanates that are industrially manufactured and commercially available are limited and the polyamideimide that can be manufactured is also limited, and it is difficult to provide a wide range of properties. On the other hand, the acid chloride method has a problem that it requires a step of eliminating HCl produced as a by-product, requires purification costs such as removal of HCl, and is expensive. JP Hei 3
No. 181511 proposes a method for producing a polyamideimide, which comprises reacting an aromatic tricarboxylic anhydride with a diamine having an ether bond in an excess of an amine component, and then reacting with a diisocyanate. Have been. Further, Japanese Patent Application Laid-Open No. 4-182466 proposes a method for producing a highly pure diimidedicarboxylic acid by reacting an aromatic diamine and trimellitic anhydride. By reacting the diimide dicarboxylic acid and diisocyanate produced using this method, it is possible to use many types of aromatic diamines as they are,
Polyamide imide can be easily synthesized without HCl by-product unlike the acid chloride method.
It is considered that a polyamideimide having a sufficient molecular weight can be synthesized with few by-products.

[0003] On the other hand, polydimethylsiloxane is composed of a main chain having high ionicity and large cohesive force, and a side chain of nonionic and weak cohesive force. It is known to take a helical structure with the inside facing. It is known that when a siloxane skeleton is introduced into a polymer, a space occupied by one polymer molecule increases due to the helical structure of the siloxane portion, and the gas permeability of the resin increases. In addition, since the siloxane skeleton undergoes severe thermal vibrations, but the interaction between the siloxane skeletons is small, it can be expected that the elastic modulus and flexibility of the resin are modified. If a siloxane skeleton can be synthesized with polyamideimide, which is a heat-resistant polymer, by an industrially advantageous isocyanate method, a heat-resistant polymer having various properties can be obtained, or generally synthesized using a high boiling point solvent. Although the drying efficiency of polyamideimide can be expected to be increased, there has been no method for obtaining a high molecular weight product.

[0004]

A method for producing a high-purity diimidedicarboxylic acid by reacting an aromatic diamine and trimellitic anhydride is disclosed in JP-A-4-182466. According to this publication, diimide dicarboxylic acid, which is the final reaction product, is hardly dissolved in the reaction solvent and precipitates, so that separation and recovery and purification of diimide dicarboxylic acid are easy, and furthermore, the aromatic hydrocarbon used is water. Because it is a solvent that can be azeotroped with water generated during the reaction,
It can be removed outside the reaction system, so that the reaction time can be shortened,
It is described that a highly pure product can be obtained. Conventionally, when a polyamideimide is produced by reacting a diimidedicarboxylic acid and a diisocyanate compound, it is necessary to react the diimidedicarboxylic acid with the diisocyanate compound after taking it out as a solid because the solubility of the diimidedicarboxylic acid is low. Polyamide imides obtained from dicarboxylic acids and diisocyanate compounds have been known in the art, and it is also known to introduce an imide ring to improve heat resistance. Therefore, these were improved, an aromatic diamine having three or more aromatic rings was selected as the aromatic diamine, and a trimellitic anhydride was reacted with the aromatic diamine to synthesize a highly soluble aromatic diimide dicarboxylic acid, which was purified in the next step. It has been proposed to react with a diisocyanate compound without performing the reaction to obtain a polyamideimide in high yield.

[0005] On the other hand, polydimethylsiloxane is composed of a main chain having high ionicity and high cohesive force and a side chain of nonionic and low cohesive force. It is known to take a helical structure with the inside facing. It is known that when a siloxane skeleton is introduced into a polymer, a space occupied by one polymer molecule increases due to the helical structure of the siloxane portion, and the gas permeability of the resin increases. For example, Japanese Patent Application Laid-Open No.
No. 429 proposes a gas separation membrane made of a polyamideimide-polysiloxane block copolymer. In addition, since the siloxane skeleton undergoes severe thermal vibrations, but the interaction between the siloxane skeletons is small, it can be expected that the elastic modulus and flexibility of the resin are modified.
If a siloxane skeleton can be introduced into a polyamideimide that is a heat-resistant polymer, it is expected that resins having various properties can be obtained and that the drying efficiency of a polyamideimide generally synthesized using a high-boiling solvent can be increased. However, there has been no method for obtaining a high molecular weight product.

When a diamine having two or less aromatic rings is used, as described in JP-A-4-182466, the resulting diimidedicarboxylic acid becomes insoluble in a synthesis solvent, and thus the diimidedicarboxylic acid At the stage, filtration must be performed, and the number of filtration steps and purification steps increases, which is a factor of cost increase. In addition, since the solubility of the purified diimide dicarboxylic acid is low, the molecular weight does not increase even if the diimide dicarboxylic acid is reacted with the diisocyanate compound. There were drawbacks such as inferiority. In the present invention, the diimide dicarboxylic acid, which is a disadvantage as described above, is soluble in a solvent, and the reaction product of the diimide dicarboxylic acid and the diisocyanate compound is also soluble in the solvent. An object of the present invention is to provide a high-molecular-weight siloxane-containing polyamideimide capable of easily forming a film by dissolving a solvent in a dissolved polyamideimide varnish, and a method for synthesizing the same.

[0007]

Means for Solving the Problems In order to solve the above-mentioned drawbacks, the present inventors have made intensive studies on the synthesis of a high-molecular-weight siloxane-containing polyamideimide which does not require a filtration step, and as a result, have reached the present invention. The present invention includes diimide dicarboxylic acids represented by the general formulas (1) and (2) obtained by reacting a mixture of a diamine and a siloxane diamine having three or more aromatic rings with trimellitic anhydride. It is a siloxane-containing polyamideimide obtained by reacting a mixture with an aliphatic or alicyclic aliphatic diisocyanate compound represented by the general formula (3).

[0008]

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[0009]

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[0010]

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The present invention also relates to a mixture of (A) diamine and (B) siloxane diamine having three or more aromatic rings (A / B = 99.9 / 0.1 to 0.1 / 99.9 molar ratio). ) And trimellitic anhydride were combined with the total moles of (A + B) / molar ratio of trimellitic anhydride = 1 / 2.05 / 1 /
2. A mixture containing the diimide dicarboxylic acid represented by the general formula (1) and the general formula (2) obtained by the reaction at 20.20 and an aliphatic or alicyclic aliphatic diisocyanate represented by the general formula (3) Compound and the total number of moles of (A + B) /
A siloxane-containing polyamideimide obtained by reacting an aliphatic or alicyclic aliphatic diisocyanate compound at a molar ratio of 1 / 1.05 to 1 / 1.50 is preferable. Further, (C) 2,2-bis [4- {4- (5-hydroxycarbonyl-1,3-dione-isoindolino) phenoxy} phenyl] propane and (D) bis (5-hydroxycarbonyl- 1,3-
Mixture of dione-isoindolino) propyl polydimethylsiloxane (C / D = 99.9 / 0.1-0.1 / 9
9.9 mole ratio) and the aliphatic or alicyclic aliphatic diisocyanate compound and the total mole number of (C + D) and the molar ratio of the aliphatic or alicyclic aliphatic diisocyanate compound to 1/1.
A siloxane-containing polyamideimide is preferred when reacted at 5 to 1 / 1.50. The present invention provides a mixture of (A) a diamine having three or more aromatic rings and (B) a siloxane diamine (A / B = 99.9 / 0.1 to 0.1).
/99.9 molar ratio) and trimellitic anhydride (A +
B) Total molar number of trimellitic anhydride and molar ratio 1 /
2.05 to 1 / 2.20 in the presence of an aprotic polar solvent in the presence of an aprotic polar solvent at a temperature of 50 to 90 ° C. 0.
A mixture containing aromatic diimide dicarboxylic acid and siloxane diimide dicarboxylic acid is produced by charging at a weight ratio of 5 and reacting at 120 to 180 ° C., and siloxane containing a mixture of the mixture with an aliphatic or alicyclic aliphatic diisocyanate. This is a method for producing a polyamideimide. Then, after the diimide dicarboxylic acid is produced, the aromatic hydrocarbon is removed from the solution, and the resultant is reacted with an aliphatic or alicyclic aliphatic diisocyanate. Further, the method for producing a siloxane-containing polyamideimide is preferably such that the aprotic polar solvent is N-methylpyrrolidone and the aromatic hydrocarbon azeotropic with water is toluene. Also, the present invention
A varnish containing a siloxane-containing polyamideimide obtained as described above.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the ratio of the total number of moles of the above aromatic diamine and siloxane diamine to 2.
A mixture of aromatic diimide dicarboxylic acid and siloxane diimide dicarboxylic acid is synthesized by reacting 05 to 2.20 times mole of trimellitic anhydride. In producing the mixture of the aromatic diimide dicarboxylic acid and the siloxane diimide dicarboxylic acid, a mixed solution of an aprotic polar solvent and an aromatic hydrocarbon capable of azeotroping with water is used. After completion of the reaction, the aromatic hydrocarbon is removed by distillation or the like, and subsequently reacted with a diisocyanate compound to produce a polyamideimide.The produced polyamideimide is dissolved in the aprotic polar solvent, and the product is used as a solvent varnish. Becomes

The diamine having three or more aromatic rings used in the present invention includes 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter abbreviated as BAPP) and bis [4- (3 -Aminophenoxy) phenyl]
Sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4-
(4-aminophenoxy) phenyl] methane, 4,4 '
-Bis (4-aminophenoxy) biphenyl, bis [4
-(4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone,
1,3-bis (4-aminophenoxy) benzene, 1,
4-bis (4-aminophenoxy) benzene and the like can be exemplified, and these can be used alone or in combination. BAPP is particularly preferred over other diamines because of the balance of properties of the polyamideimide and cost.

The siloxane diamine used in the present invention is represented by the general formula (4).

[0015]

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Examples of such a siloxane diamine include those represented by the following formula (5). Among them, amino-modified reactive silicone oil X-22-161AS (amine equivalent 45
0), X-22-161A (amine equivalent 840), X-
22-161B (amine equivalent 1500), trade name, manufactured by Shin-Etsu Chemical Co., Ltd., BY16-853 (amine equivalent 650), BY16-853B (amine equivalent 2200)
As mentioned above, commercial names include the trade names of Toray Dow Corning Silicone Co., Ltd.

[0017]

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A mixture of these diamines having three or more aromatic rings and siloxane diamine is reacted with trimellitic anhydride (hereinafter abbreviated as TMA). The mixed solvent used in the production method of the present invention is an organic solvent that does not react with a diamine having three or more aromatic rings, siloxane diamine and TMA, and the type of mixed solution used and the mixing ratio thereof are important. Examples of the aprotic polar solvent used in the present invention include dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, 4-butyrolactone, sulfolane, cyclohexanone and the like. N-methyl-2-methylpyrrolidone (hereinafter abbreviated as NMP), which has a high boiling point because an imidation reaction requires a high temperature, is particularly preferable. The amount of water contained in these mixed solvents is controlled to 0.2% by weight or less because trimellitic acid generated by hydration of TMA does not sufficiently promote the reaction and causes a decrease in the molecular weight of the polymer. Is preferred. The aprotic polar solvent used in the present invention is not particularly limited, but if the weight ratio of the total of the diamine having three or more aromatic rings and trimellitic anhydride is large, the solubility of TMA decreases. If the reaction cannot be carried out sufficiently, or if it is too low, it is disadvantageous for an industrial production method, the content is preferably in the range of 10% by weight to 70% by weight.

The aromatic hydrocarbons azeotropic with water used in the present invention include benzene, xylene, ethylbenzene,
Aromatic hydrocarbons such as toluene can be exemplified. Particularly, toluene having a relatively low boiling point and less harmful to the working environment is preferable, and the amount used is 0.1 to 0.5 of the aprotic polar solvent.
The range of the weight ratio (10 to 50% by weight) is preferable. When the amount of the aromatic hydrocarbon used is less than the above range, the effect of removing water by azeotropic distillation is reduced, and the promotion of the production of diimidedicarboxylic acid is also reduced. If the amount of the aromatic hydrocarbon used exceeds the above range, the aromatic amide carboxylic acid as a reaction intermediate or the generated aromatic diimide dicarboxylic acid may be precipitated. During the reaction, the aromatic hydrocarbon is made to azeotrope with water and is allowed to flow out of the system. For this reason, the amount of aromatic hydrocarbons in the solvent may decrease. Therefore, in order to maintain the amount of the aromatic hydrocarbon solvent present in the reaction system at a constant rate, the solvent flowing out of the system is separated from water using, for example, a cock-equipped water content receiver or the like, and then separated into water. It is preferable to perform a method of returning or supplementing.

The reaction conditions in the present invention are as follows. First, the reaction of a diamine having three or more aromatic rings and a siloxane diamine with trimellitic anhydride is carried out at 50 to 90 ° C. in the presence of an aprotic polar solvent. There must be. After this reaction, an aromatic hydrocarbon is charged and reacted at a temperature azeotropic with water. The reaction temperature at this time varies depending on the amount of the aromatic hydrocarbons and the capacity of the moisture meter with a cock. The reaction is carried out until water is no longer produced as a by-product in the reaction system, and it is particularly preferable to confirm that the theoretical amount of water has been distilled off.

The reaction solution may contain an aromatic hydrocarbon. However, after the above reaction, the temperature is increased to react with an aliphatic or alicyclic aliphatic diisocyanate compound.
It is preferable to further raise the temperature to distill off the aromatic hydrocarbons before performing the next reaction. The resulting mixture of aromatic diimide dicarboxylic acid and siloxane diimide dicarboxylic acid can be reacted with a diisocyanate compound to produce a siloxane-containing polyamideimide having a high molecular weight. Examples of the aliphatic or alicyclic aliphatic diisocyanate compound represented by the general formula (Formula 3) used in the present invention include hexamethylene diisocyanate, isophorone diisocyanate, and methylene bis (cyclohexyl diisocyanate). These can be used alone or in combination. If the reaction temperature is too low, the reaction time is prolonged. If the reaction temperature is too high, the diisocyanate compounds react with each other.
Preferably, the reaction is carried out at a temperature of up to 200C. Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

[0022]

【Example】

(Example 1) 25 ml with a cock connected to a reflux condenser
BAPP (2,2-bis [4- (4-aminophenoxy) phenyl] propane as a diamine having three or more aromatic rings in a 1-liter separable flask equipped with a water quantification receiver, a thermometer, and a stirrer. ) 65.7 g (0.16
Mol), 33.3 g (0.04 mol) of reactive silicone oil X-22-161AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 416) as siloxane diamine,
80.7 g (0.42 mol) of TMA (trimellitic anhydride) and 560 g of NMP (N-methyl-2-pyrrolidone) as an aprotic polar solvent were charged.
Stirred for minutes. Then, 100 ml of toluene was charged as an aromatic hydrocarbon capable of azeotropic distillation with water, and then the temperature was increased to about 1
Reflux at 60 ° C. for 2 hours. Water is about 7.
After confirming that no more than 2 ml of water had accumulated and that no outflow of water was observed, the temperature was increased to about 190 ° C. while removing the outflow liquid accumulated in the water content measurement receiver to remove toluene. Thereafter, the solution is returned to room temperature, and IP is obtained as an aliphatic or alicyclic aliphatic diisocyanate compound.
53.3 g (0.24 mol) of DI (isophorone diisocyanate) (manufactured by Huls Japan K.K.) was added,
The reaction was performed at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of the siloxane-containing polyamideimide was obtained. After applying this solution varnish to a glass plate and drying at 150 ° C. for 30 minutes,
The film was peeled off from the glass plate.
Heating was carried out for a time to obtain a siloxane-containing polyamideimide film having a thickness of about 60 μm. The glass transition temperature, tensile strength, elongation at break and tensile modulus at room temperature of this film were measured. Further, the molecular weight of the obtained siloxane-containing polyamideimide was measured, and the results are shown in Table 1.
It was shown to. The glass transition temperature was determined using the obtained film as D
VE (Wide-area dynamic viscoelasticity measurement device, measurement frequency 10 Hz)
The value of the maximum value of tan δ was used. The tensile strength, elongation at break and tensile modulus at room temperature were measured by cutting the obtained film into strips having a width of 10 mm and using a tensile tester at a crosshead speed of 50 mm / min. For the molecular weight, 50 mg of the obtained varnish was sampled, and dimethylformamide / tetrahydrofuran = 1/1 (volume ratio, containing phosphoric acid 0.06 M, lithium bromide 0.03 M)
5 ml of the solution was added and the solution was measured by GPC, and the value was calculated by converting to standard polystyrene.

Example 2 A diamine having three or more aromatic rings was prepared as a diamine having three or more aromatic rings in a 1-liter separable flask equipped with a faucet connected to a reflux cooler and having a 25-ml water-quantification receiver, a thermometer, and a stirrer. 2,2-bis [4- (4
-Aminophenoxy) phenyl] propane) 32.8 g
(0.08 mol), 31.7 g of reactive silicon oil X-22-161A (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 792) as siloxane diamine (0.02 mol)
Mol), TMA (trimellitic anhydride) 40.3 g
(0.21 mol) as NM as an aprotic polar solvent
315 g of P (N-methylpyrrolidone) was charged,
For 30 minutes. Then, 100 ml of toluene was charged as an aromatic hydrocarbon capable of azeotropic distillation with water, and then the temperature was increased and the mixture was refluxed at about 160 ° C. for 2 hours. Make sure that about 3.6 ml of water has accumulated in the receiver for water content and that no outflow of water has been seen, and remove the effluent remaining in the receiver for water content to about 190 ° C. The temperature was increased to remove the toluene. After that, the solution is returned to room temperature,
Hexamethylene diisocyanate (manufactured by Nippon Polyurethane Co., Ltd.) (20.2 g, 0.12 mol) was charged as an aliphatic or alicyclic aliphatic diisocyanate compound.
The reaction was performed at 90 ° C. for 2 hours. After completion of the reaction, an NMP solution of the siloxane-containing polyamideimide was obtained. This solution was formed into a film in the same manner as in Example 1, and the properties are shown in Table 1.

(Examples 3 to 6) A diamine having three or more aromatic rings was prepared in a 1-liter separable flask equipped with a faucet connected to a reflux condenser and having a 25 ml water content receiver, a thermometer and a stirrer. BAPP (2,2-bis [4-
(4-aminophenoxy) phenyl] propane), a reactive silicone oil X-22-
161AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent: 416), TMA (trimellitic anhydride), and NMP (N-methyl-2-pyrrolidone) as an aprotic polar solvent at the compounding ratios shown in Table 2, respectively. It stirred and stirred at 80 degreeC for 30 minutes. Then, 100 ml of toluene was charged as an aromatic hydrocarbon capable of azeotropic distillation with water, and then the temperature was increased and the mixture was refluxed at about 160 ° C. for 2 hours. Make sure that about 3.6 ml of water has accumulated in the receiver for water content and that no outflow of water has been seen, and remove the effluent remaining in the receiver for water content to about 190 ° C. The temperature was increased to remove the toluene. After that, the solution is returned to room temperature,
As an aliphatic or alicyclic aliphatic diisocyanate compound, IPDI (isophorone diisocyanate) (manufactured by Huls Japan KK) was added in the amount shown in Table 2, and 19
The reaction was performed at 0 ° C. for 2 hours. After completion of the reaction, an NMP solution of the siloxane-containing polyamideimide was obtained. The molecular weight of the obtained siloxane-containing polyamideimide was measured and is shown in Table 2.

(Comparative Example) 1 equipped with a 25 ml water quantification receiver with a cock connected to a reflux cooler, a thermometer, and a stirrer
4,4'-diaminodiphenylmethane 3 as a diamine having two aromatic rings in a liter separable flask
9.6 g (0.2 mol), 41.6 g of reactive silicone oil X-22-161AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 416) as siloxane diamine
(0.05 mol), TMA (trimellitic anhydride) 9
6.1 g (0.5 mol) and 700 g of NMP (N-methyl-2-pyrrolidone) as an aprotic polar solvent were charged and stirred at 80 ° C. for 30 minutes. Then, 100 ml of toluene was charged as an aromatic hydrocarbon capable of azeotropic distillation with water, and then the temperature was increased and the mixture was refluxed at about 160 ° C. for 2 hours. With the outflow of water, a reaction product was deposited. Make sure that about 9 ml of water has accumulated in the receiver for water content and that no outflow of water has been observed. Raised to remove toluene. However, the precipitated aromatic diimide dicarboxylic acid did not dissolve, and no solution was obtained.
Thereafter, the solution is returned to room temperature, and IPDI (isophorone diisocyanate) (manufactured by Huls Japan Ltd.) 5 is used as an aliphatic or alicyclic aliphatic diisocyanate compound.
5.5 g (0.25 mol) was charged and reacted at 170 ° C. for 2 hours. However, the precipitate was not dissolved and was not further reacted.

[0026]

[Table 1] Item Example 1 Example 2 Glass transition temperature (° C.) 195 210 Tensile strength (kg / mm ² ) 8.2 9.2 Elongation at break (%) 14 14 Tensile modulus (MPa) 2200 2300 Molecular weight (weight average) 69000 72000

[0027]

[Table 2] Item BAPP 161AS TMA NMP IPDI Molecular weight Example 3 0.16 0.04 0.44 320 0.26 66000 Example 4 0.14 0.06 0.42 320 0.24 71000 Example 5 0.12 0.08 0.42 340 0.24 64000 Example 6 0.10 0.10 0.42 350 0.24 66000 BAPP: (2,2-bis [4- (4-aminophenoxy) phenyl] propane) 161AS: Reactive silicon oil X-22-161AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent: 416) TMA: anhydrous Trimellitic acid NMP: N-methylpyrrolidone IPDI: Isophorone diisocyanate BAPP, reactive silicone oil X-22-161AS, TMA, IPDI Numerical values indicate molar NMP (g), and molecular weight indicates weight average molecular weight.

[0028]

Industrial Applicability The siloxane-containing polyamideimide and the solution varnish containing the same and the method for producing the same according to the present invention can be used for varnishes, adhesives and adhesive films which require heat resistance. Field, automotive field,
It can be widely used in construction and building materials. And, compared to the conventional production method, siloxane diimide dicarboxylic acid and aromatic diimide dicarboxylic acid are soluble in a solvent, and a siloxane-containing polyamideimide obtained by reacting it with an aliphatic or alicyclic aliphatic diisocyanate compound. Is also soluble in solvents and can be applied to a wide range of applications. Further, since it is soluble in a solvent, a filtration or purification step is not required, and a siloxane-containing polyamideimide having a large molecular weight can be produced, so that it is excellent in film forming properties and resin properties and is industrially useful. The obtained siloxane-containing polyamideimide has a high solvent drying property and is advantageous in forming a film or a coating film.

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[Procedure amendment]

[Submission date] February 24, 1998

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[0015]

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[Procedure amendment]

[Submission date] October 28, 1998

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[0009]

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A mixture of these diamines having three or more aromatic rings and siloxane diamine is reacted with trimellitic anhydride (hereinafter abbreviated as TMA). The mixed solvent used in the production method of the present invention is an organic solvent that does not react with a diamine having three or more aromatic rings, siloxane diamine and TMA, and the type of mixed solution used and the mixing ratio thereof are important. Examples of the aprotic polar solvent used in the present invention include dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, 4-butyrolactone, sulfolane, cyclohexanone and the like. The imidization reaction, a high boiling point for requiring high temperatures, N- methyl-2 - Pi pyrrolidone (hereinafter NM
P) is particularly preferred. The amount of water contained in these mixed solvents is controlled to 0.2% by weight or less because trimellitic acid generated by hydration of TMA does not sufficiently promote the reaction and causes a decrease in the molecular weight of the polymer. Is preferred. The aprotic polar solvent used in the present invention is not particularly limited, but if the weight ratio of the total of the diamine having three or more aromatic rings and trimellitic anhydride is large, the solubility of TMA decreases. If the reaction cannot be carried out sufficiently, or if it is too low, it is disadvantageous for an industrial production method, the content is preferably in the range of 10% by weight to 70% by weight.

Claims (7)

[Claims] 1. A diimide dicarboxylic acid represented by the general formula (1) and the general formula (2) obtained by reacting a mixture of a diamine having at least three aromatic rings and a siloxane diamine with trimellitic anhydride. A siloxane-containing polyamideimide obtained by reacting a mixture containing the compound with an aliphatic or alicyclic aliphatic diisocyanate compound represented by the general formula (3). Embedded image Embedded image Embedded image 2. A mixture of (A) diamine and (B) siloxane diamine having three or more aromatic rings (A / B = 9)
9.9 / 0.1 to 0.1 / 99.9 mole ratio) and trimellitic anhydride in a total mole number of (A + B) and a mole ratio of trimellitic anhydride of 1 / 2.05 to 1/2. The mixture containing the diimidedicarboxylic acid represented by the general formula (1) and the general formula (2) obtained by reacting
A siloxane-containing polyamide obtained by reacting an aliphatic or alicyclic aliphatic diisocyanate compound represented by the formula) with a total mole number of (A + B) and a molar ratio of diisocyanate of 1 / 1.05 to 1 / 1.50 Imide. 3. An aromatic diimide dicarboxylic acid comprising (C) 2,2-bis [4- {4- (5-hydroxycarbonyl-1,3-dione-isoindolino) phenoxy} phenyl] propane and (D) bis ( Mixture of 5-hydroxycarbonyl-1,3-dione-isoindolino) propyl polydimethylsiloxane (C / D = 99.9)
/0.1 to 0/100 mole ratio) and the aliphatic or alicyclic aliphatic diisocyanate compound and the total mole number of (C + D) and the mole ratio of diisocyanate compound 1 / 1.05 to 1 /
1. A siloxane-containing polyamideimide obtained by a reaction at 1.50. 4. A mixture of (A) a diamine having three or more aromatic rings and (B) a siloxane diamine (A / B = 9)
9.9 / 0.1 to 0.1 / 99.9 mole ratio) and trimellitic anhydride in the total mole number of (A + B) and the mole ratio of trimellitic anhydride 1 / 2.05 to 1/2. In step 20, the reaction is carried out at 50 to 90 ° C. in the presence of an aprotic polar solvent, and an aromatic hydrocarbon which can be azeotroped with water is added at a weight ratio of 0.1 to 0.5 of the aprotic polar solvent. , 120-180
C. to produce a mixture containing an aromatic diimide dicarboxylic acid and a siloxane diimide dicarboxylic acid, and reacting the mixture with an aliphatic or alicyclic aliphatic diisocyanate compound represented by the general formula (3). A method for producing a siloxane-containing polyamideimide, which is characterized in that: 5. The method for producing a siloxane-containing polyamideimide according to claim 4, wherein after producing the diimide dicarboxylic acid, the aromatic hydrocarbon is removed from the solution, and the resultant is reacted with a diisocyanate compound. 6. The method for producing a siloxane-containing polyamideimide according to claim 4, wherein the aprotic polar solvent is N-methylpyrrolidone, and the aromatic hydrocarbon azeotropic with water is toluene. 7. A varnish containing a siloxane-containing polyamideimide obtained by the method according to claim 4. Description: