JP2000239340A - Production of polyamideimide, polyamideimide produced thereby and varnish containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymideimide capable of keeping high elastic modulus even at a high temperature above the glass transition temperature by reacting a diamine with trimellitic anhydride in the presence of a specific solvent, subjecting the product to cyclodehydration and reacting the product with a diisocyanate in the presence of an aromatic dicarboxylic acid. SOLUTION: The objective polymer can be produced by reacting a diamine at least containing the compound of the formula: H2N-R1-NH2 [R1 is a group of formula I; R2 and R3 are each a bivalent organic group; R4 to R7 are each an alkyl or a (substituted) phenol; (n) is 1-50] with trimellitic anhydride in the presence of an aprotic polar solvent such as N-methyl-2-pyrrolidone, subjecting the produced amic acid to cyclodehydration to obtain a diimide dicarboxylic acid and reacting the product with a diisocyanate preferably expressed by the formula: OCN-R8-NCO (R8 is a group of formula II or the like) in the presence of an aromatic dicarboxylic acid such as terephthalic acid. The polymer is useful for varnish, adhesive, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polyamideimide obtained by reacting a diamine with trimellitic anhydride and then reacting it with a diisocyanate, a polyamideimide obtained thereby, and a varnish containing the same.

[0002]

2. Description of the Related Art Polyamideimide is a resin having excellent electrical properties such as volume resistance and dielectric breakdown strength, and has recently been used for various purposes including wiring boards. Polyamide imide is usually synthesized by an isocyanate method based on a reaction between trimellitic anhydride and an aromatic diisocyanate, or an acid chloride method based on a reaction between an aromatic diamine and trimellitic acid chloride. 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-A-3-181511 discloses the production of polyamideimide characterized by a two-stage method comprising 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. A method has been proposed. In addition, Japanese Unexamined Patent Publication No.
JP-A-182466 proposes a method for producing a high-purity diimidedicarboxylic acid by reacting an aromatic diamine and trimellitic anhydride. By reacting diimide dicarboxylic acid and diisocyanate produced using this method, it is possible to use many kinds of aromatic diamines as they are, without easily producing HCl as in the acid chloride method, polyamide easily. It is considered that an imide can be synthesized, and a polyamideimide having a sufficient molecular weight with few by-products can be synthesized.

It is well known that a wholly aromatic polyamide has high orientation and excellent fiber and film moldability, and has high heat resistance due to packing between polymer chains. Usually, this wholly aromatic polyamide is synthesized by condensation of an aromatic dicarboxylic acid chloride and an aromatic diamine, or by an isocyanate method by a reaction between an aromatic dicarboxylic acid and an aromatic diisocyanate. In particular, the isocyanate method, which is advantageous in cost because it has few by-products and does not require purification, has almost the same reaction conditions as the above-mentioned polyamideimide. For this reason, it is conceivable that a polyamideimide having improved heat resistance can be synthesized by reacting a mixture of diimide dicarboxylic acid and aromatic dicarboxylic acid with diisocyanate.

[0004] 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 bond pointing inward. 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. Therefore, if a siloxane structure can be introduced into a heat-resistant polymer by an industrially advantageous isocyanate method, a heat-resistant polymer having various characteristics can be obtained or synthesized using a high boiling point solvent in general. Can be expected to increase the drying efficiency of the polyamideimide.

[0005]

Problems to be Solved by the Invention
No. 7 proposes synthesizing a siloxane-containing polyamideimide by polycondensing an aromatic tricarboxylic anhydride, an aromatic diisocyanate, and a diaminosiloxane. However, the resin obtained by this method is inferior in film formability, the film is brittle, and also has insufficient heat resistance, so that the temperature above the glass transition point,
For example, mechanical properties such as an elastic modulus at a high temperature of 200 ° C. or higher are not sufficient. In Japanese Patent Application Laid-Open No. 4-264003, a siloxane-containing polyamide or a siloxane-containing polyamideimide is synthesized by polycondensing an aromatic dicarboxylic acid or an aromatic tricarboxylic acid with diaminosiloxane. Since a condensing agent is required, it is difficult to completely remove by-product HCl, and monomers and oligomers are mixed in by side reactions, various characteristics, especially volume resistance, after moisture absorption, Electrical characteristics such as insulation resistance are not sufficient. To improve these drawbacks, a mixture of a diamine containing at least three aromatic rings and a siloxane diamine and trimellitic anhydride are reacted with an azeotropic hydrocarbon with water in an aprotic polar solvent to form by-produced water. Is distilled off to synthesize a highly soluble aromatic diimide dicarboxylic acid, which is further reacted with diisocyanate to synthesize a high molecular weight polyamide imide. However, the siloxane-containing polyamideimide obtained by this method also has a remarkable decrease in the elastic modulus at a high temperature, and the mechanical properties at a temperature higher than the glass transition point are extremely reduced. An object of the present invention is to provide a method for producing a polyamideimide capable of maintaining a high elastic modulus even at a high temperature equal to or higher than the glass transition point, a polyamideimide obtained by the method, and a varnish containing the same, in order to solve the above-described disadvantages. did.

[0006]

Means for Solving the Problems In order to solve the above-mentioned drawbacks, the present inventors have conducted intensive studies on the synthesis of a resin capable of maintaining a high elastic modulus even at a high temperature higher than the glass transition point, and as a result, have reached the present invention. The present invention is obtained by reacting a diamine and trimellitic anhydride in the presence of an aprotic polar solvent to obtain an amic acid, and then producing a diimide dicarboxylic acid by dehydration and ring closure, and reacting this with a diisocyanate. This is a method for producing a polyamideimide obtained by allowing an aromatic dicarboxylic acid to coexist with a diimidedicarboxylic acid in the resulting polyamideimide and reacting the diisocyanate.

Further, the present invention provides a polyamide imide wherein the diamine is at least a diamine containing a siloxane diamine represented by the general formula (1), and the diisocyanate is an aromatic diisocyanate represented by the general formula (2). It is a manufacturing method of. That is, in the presence of an aprotic polar solvent, at least a diamine containing a siloxane diamine represented by the general formula (Formula 1) is reacted with trimellitic anhydride to form an amide acid, and then dehydrated and closed to form a diimidedicarboxylic acid. It is a preferable method for producing a polyamide imide, in which an aromatic dicarboxylic acid is allowed to coexist with this, and the aromatic diisocyanate represented by the general formula (2) is reacted.

[0008]

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[0009]

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The present invention further relates to a mixture (A) of (A) a siloxane diamine represented by the general formula (1) and (B) an aromatic diamine having three or more aromatic rings represented by the general formula (3). /B=100.0/0.0 to 0.1 / 99.9 molar ratio) and trimellitic anhydride to produce diimidedicarboxylic acid, which is reacted with an aromatic compound represented by the general formula (4). It is a preferable method for producing a polyamideimide when a dicarboxylic acid is allowed to coexist and is reacted with an aromatic diisocyanate represented by the general formula (2).

[0011]

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[0012]

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Further, the present invention is a method for producing a polyamideimide, which is preferably carried out in the presence of a basic catalyst when reacting diimidedicarboxylic acid and aromatic dicarboxylic acid with diisocyanate. Further, the present invention is a method for producing a polyamideimide, which preferably uses a trialkylamine represented by the general formula (5) as a basic catalyst. Further, the present invention is a polyamideimide obtained by the method for producing a polyamideimide described above. Further, the present invention is a varnish containing a polyamideimide obtained as described above.

[0014]

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[0015]

BEST MODE FOR CARRYING OUT THE INVENTION A mixture of diamines is reacted with trimellitic anhydride in the presence of an aprotic polar solvent to obtain a diimidedicarboxylic acid as a reaction product.
A method of synthesizing a polyamide imide by reacting with a diisocyanate in the next step is known, and the present invention provides a method for producing a diimide dicarboxylic acid, and then allowing an aromatic dicarboxylic acid to coexist and reacting the diisocyanate.
A polyamideimide capable of maintaining a high elastic modulus even in a high temperature region equal to or higher than the glass transition point, for example, a high temperature region equal to or higher than 200 ° C. can be produced. In the present invention, in the presence of an aprotic polar solvent, a diamine and trimellitic anhydride are reacted to form an amide acid, and then dehydrated and ring-closed to produce a diimide dicarboxylic acid, which is further coexisted with an aromatic dicarboxylic acid. And reacting with a diisocyanate.

In the present invention, it is preferable to synthesize a diimidedicarboxylic acid by reacting trimellitic anhydride in a molar amount of 1.80 to 2.20 times the total number of moles of the mixture of diamines. In producing this diimide dicarboxylic acid, in the presence of an aprotic polar solvent, 50 to 90
C., and further reacted with aprotic polar solvent of 0.1 to
Aromatic hydrocarbon is added at a weight ratio of 0.5 (10% to 50% by weight), and the reaction is performed at 120 to 180 ° C. After completion of the reaction, the aromatic hydrocarbons are removed by distillation or the like, and subsequently,
An aromatic dicarboxylic acid is added and reacted with a diisocyanate to produce a siloxane-containing polyamideimide. The produced polyamideimide is dissolved in the aprotic polar solvent described above, and can be used as a varnish of the solvent to produce a product.

The siloxane diamine used in the present invention is represented by the general formula (1). Examples of such siloxane diamines include those represented by the following formula (6). Among them, amino-modified reactive silicone oil X-22 which is a dimethylsiloxane-based terminal amine
-161AS (amine equivalent 450), X-22-161A
(Amine equivalent: 840), X-22-161B (Amine equivalent: 1500), trade name: BY1 manufactured by Shin-Etsu Chemical Co., Ltd.
6-853 (amine equivalent 650), BY16-853B
(Amine equivalent: 2200), and the trade names of Toray Dow Corning Silicone Co., Ltd. mentioned above are listed as commercial products.

[0018]

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The diamine having three or more aromatic rings represented by the general formula (3) used in the present invention includes 2,2-
Bis [4- (4-aminophenoxy) phenylpropane (hereinafter abbreviated as BAPP), 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.

These siloxane diamines are used alone, or a mixture of these siloxane diamines and a diamine having three or more aromatic rings is reacted with trimellitic anhydride (hereinafter abbreviated as TMA). The aprotic polar solvent used in the production method of the present invention is an organic solvent that does not react with diamine and TMA, and the type of solvent used and its mixing ratio are important. Examples of the aprotic polar solvent used in the present invention include dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, 4-butyrolactone, sulfolane, cyclohexane and the like. For the imidization reaction, N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), which has a high boiling point due to its high temperature, is particularly preferred. The amount of water contained in these solvents depends on the trimellitic acid generated by hydration of TMA,
Since the reaction does not proceed sufficiently and causes a decrease in the molecular weight of the polymer, the content is preferably controlled to 0.2% by weight or less. Further, the aprotic polar solvent used in the present invention,
Although not particularly limited, the ratio of the total weight of the diamine and trimellitic anhydride may be too high to lower the solubility of trimellitic anhydride to perform a sufficient reaction, and if it is low, it is disadvantageous as an industrial production method. Therefore, 10% by weight or more
It is preferably in the range of 70% by weight.

In the present invention, in order to remove water efficiently, it is preferable to add an aromatic hydrocarbon capable of azeotropic distillation with water to an aprotic polar solvent to cause a reaction. As aromatic hydrocarbons azeotropic with water, benzene, xylene, ethylbenzene,
Aromatic hydrocarbons such as toluene can be exemplified. In particular, toluene having a relatively low boiling point and less harmful to the working environment is preferable. The amount used is 0.1 to 0.5 weight ratio (10 to 10) of the aprotic solvent. 50% by weight). 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 diimide dicarboxylic acid produced 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.
In the reaction of the trimellitic anhydride with at least one diamine, the reaction must be carried out at 50 to 90 ° C. in the presence of an aprotic polar solvent. After this reaction, an aromatic hydrocarbon capable of azeotroping with water 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 aromatic hydrocarbons. However, after the above reaction, the temperature is raised to react with the aromatic diisocyanate. The following reaction is preferably performed. An aromatic polyamideimide can be produced by adding an aromatic dicarboxylic acid to the resulting mixture of diimide dicarboxylic acids and reacting the mixture with an aromatic diisocyanate. The aromatic dicarboxylic acid represented by the general formula (4) used in the present invention includes terephthalic acid, isophthalic acid,
(4,4-dicarboxyl) diphenyl ether,
(4,4-dicarboxyl) diphenyl sulfone,
(4,4-dicarboxyl) benzophenone, (3,3
-Dicarboxyl) benzophenone, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and the like. In addition, dicarboxylic acids such as adipic acid and hexamethylene dicarboxylic acid can be used in combination. In particular, terephthalic acid is particularly preferable because the molecular shape is linear, so that the orientation of the produced polymer is improved and the film formability and heat resistance are good. Specific examples of the aromatic diisocyanate represented by the general formula (Formula 2) used in the present invention include 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate. Examples include isocyanate, naphthalene-1,5-diisocyanate, o-, m-xylylene diisocyanate, 2,4-tolylene dimer and the like. Also, hexamethylene diisocyanate,
Isocyanates such as 4,4′-methylenebis (cyclohexyl isocyanate) and ishiphorone diisocyanate can be used alone or in combination. In particular
MDI is preferred because isocyanate groups are separated in the molecular structure, the concentration of amide groups and imide groups in the molecule of polyamideimide becomes relatively low, and the solubility is improved.

In the present invention, when reacting a mixture of a diimide dicarboxylic acid and a mixture of dicarboxylic acids with an aromatic diisocyanate in the presence of a basic catalyst, the reaction is accelerated, and the reaction is carried out at a lower temperature. Since the polymerization can be performed, a side reaction hardly occurs, and a high molecular weight polyamideimide can be obtained. Examples of the base catalyst used herein include trimethylamine, triethylamine, tripropylamine, tri (2-ethylhexyl) amine and trioctylamine represented by the general formula (5).
In addition, pyridine, 3,5-dimethylpyridine, 2,6
-Dimethylpyridine, 2,6-dibutylpyridine, 2,
Examples thereof include 6-tri (2-ethylhexyl) pyridine. In addition, basic catalysts such as triallylamine, tetramethylethylenediamine, and pyrazine can also be used. In particular, triethylamine represented by the general formula (Formula 5) has an appropriate basicity for accelerating the polymerization reaction, and has a low boiling point, so that it can be easily removed by heating or reducing the pressure after polymerization. preferable. When the reaction temperature is low, the reaction time is prolonged. When the reaction temperature is too high, isocyanates react with each other. Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

[0025]

EXAMPLES Example 1 A 25 ml water content receiver with a cock connected to a reflux condenser, a thermometer, and a stirrer were provided.
57.1 g of reactive silicone oil X-22-161AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 408) as a siloxane diamine in a separable flask of L
(0.07 mol), TMA (trimellitic anhydride) 2
8.2 g (0.147 mol), NMP (N-methyl-2
-Pyrrolidone) and stirred at 80 ° C. for 30 minutes. After 100 ml of toluene was added, the temperature was increased and the mixture was refluxed at about 160 ° C. for 2 hours. Confirm that water has accumulated in the receiver for water determination at least about 2.5 ml, and that no outflow of water has been observed. The temperature was increased to remove the toluene. Thereafter, the solution was returned to room temperature, the receiver for determining the amount of water was removed, and 11.6 g (0.07 mol) of terephthalic acid as an aromatic dicarboxylic acid and 40.3 g of MDI (4,4-diphenylmethane diisocyanate) as an aromatic diisocyanate were added. .161 mol), 2.1 g (0.021 mol) of triethylamine (TMA)
And reacted at 110 ° C. for 2 hours. After the reaction,
An NMP solution of the siloxane-containing polyamideimide was obtained.

This solution varnish is applied to a glass plate and
After drying at 30 ° C. for 30 minutes, the film was peeled off from the glass plate, and further heated at 180 ° C. for 1 hour to a thickness of about 100 μm.
A siloxane-containing polyamideimide film was obtained.
Then, the glass transition temperature, the high-temperature elastic modulus at 200 ° C. and 250 ° C. of this film were measured. In addition, the molecular weight of the obtained siloxane-containing polyamideimide was measured, and the results are shown in Table 1. As the glass transition temperature, the maximum value of tan δ was used with a DVE wide-range dynamic viscoelasticity measuring apparatus (measuring frequency 10 Hz) using the obtained film.
The high temperature elastic modulus was also measured by a DVE wide area dynamic viscoelasticity measuring device (measuring frequency 10 Hz). The drying property of the resin is as follows.
After drying for minutes, the obtained film was evaluated by measuring the residual solvent content. The molecular weight is 50 mg of the varnish obtained.
Was collected, 5 ml of a solution of dimethylformamide / tetrahydrofuran = 1/1 (volume ratio, containing 0.06 M of phosphoric acid and 0.03 M of lithium bromide) was added, and the resulting solution was measured by GPC and calculated in terms of standard polystyrene.

(Example 2) BAPP (diamine having three or more aromatic rings in a 1-liter separable flask equipped with a faucet connected to a reflux condenser and having a 25 ml water content receiver equipped with a cock, a thermometer and a stirrer) was used. 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane) 14.4 g
(0.035 mol), 28.6 g of reactive silicone oil X-22-161AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 408) as siloxane diamine (0.
035 mol), TMA (trimellitic anhydride) 28.2
g (0.147 mol) and 245 g of NMP (N-methyl-2-pyrrolidone) were charged and stirred at 80 ° C. for 30 minutes. After 100 ml of toluene was added, the temperature was increased and the mixture was refluxed at about 160 ° C. for 2 hours. Confirm that water has accumulated in the receiver for water determination at least about 2.5 ml, and that no outflow of water has been observed. The temperature was increased to remove the toluene. After that, the solution is returned to room temperature,
After removing the water content receiver, 11.6 g (0.07 mol) of terephthalic acid was used as the aromatic dicarboxylic acid, 40.3 g (0.161 mol) of MDI (4,4-diphenylmethane diisocyanate) was used as the aromatic diisocyanate, and triethylamine was used. 1 g (0.021 mol) was charged, and 11
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. This solution was formed into a film in the same manner as in Example 1, and the properties are shown in Table 1.

(Example 3) BAPP (diamine having three or more aromatic rings 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) was used. 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane) 26.7 g
(0.065 mol), 4.1 g (0.0) of reactive silicone oil X-22-161AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 408) as siloxane diamine
05 mol), 28.2 g of TMA (trimellitic anhydride)
(0.147 mol) and 245 g of NMP (N-methyl-2-pyrrolidone) were stirred and stirred at 80 ° C. for 30 minutes.
After 100 ml of toluene was added, the temperature was increased and the mixture was refluxed at about 160 ° C. for 2 hours. Confirm that water has accumulated in the receiver for water determination at least about 2.5 ml, and that no outflow of water has been observed. The temperature was increased to remove the toluene. After that, the solution is returned to room temperature,
After removing the water content receiver, 11.6 g (0.07 mol) of terephthalic acid was used as the aromatic dicarboxylic acid, 40.3 g (0.161 mol) of MDI (4,4-diphenylmethane diisocyanate) was used as the aromatic diisocyanate, and triethylamine was used. 1 g (0.021 mol) was charged, and 11
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. This solution was formed into a film in the same manner as in Example 1, and the properties are shown in Table 1.

(Example 4) BAPP (diamine having three or more aromatic rings) 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. 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane) 14.4 g
(0.035 mol), 28.6 g of reactive silicone oil X-22-161AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 408) as siloxane diamine (0.
035 mol), TMA (trimellitic anhydride) 28.2
g (0.147 mol) and 245 g of NMP (N-methyl-2-pyrrolidone) were charged and stirred at 80 ° C. for 30 minutes. After 100 ml of toluene was added, the temperature was increased and the mixture was refluxed at about 160 ° C. for 2 hours. Confirm that water has accumulated in the receiver for water determination at least about 2.5 ml, and that no outflow of water has been observed. The temperature was increased to remove the toluene. After that, the solution is returned to room temperature,
The moisture meter was removed, and 11.6 g (0.07 mol) of terephthalic acid as an aromatic dicarboxylic acid and 40.3 g (0.161 mol) of MDI (4,4-diphenylmethane diisocyanate) as an aromatic diisocyanate were added. The reaction was performed at 170 ° C. for 2 hours without adding triethylamine. 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.

Comparative Example 1 As a comparative example of Example 1, the same synthesis was performed without using an aromatic dicarboxylic acid, and the characteristics were evaluated. Reactive silicon oil X-22-161AS as siloxane diamine 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 (a product of Shin-Etsu Chemical Co., Ltd.) Name, amine equivalent 408) 57.1 g (0.0
7 mol), 28.2 g of TMA (trimellitic anhydride)
(0.147 mol), 245 g of NMP (N-methyl-2-pyrrolidone) were charged and stirred at 80 ° C. for 30 minutes. After 100 ml of toluene was added, the temperature was increased and the mixture was refluxed at about 160 ° C. for 2 hours. Confirm that water has accumulated in the receiver for water determination at least about 2.5 ml, and that no outflow of water has been observed. The temperature was increased to remove the toluene. After that, the solution is returned to room temperature,
Remove the moisture meter receiver and use MDI (4,4-diphenylmethane diisocyanate) as the aromatic diisocyanate
20.3 g (0.081 mol), triethylamine
1 g (0.021 mol) was charged and reacted at 110 ° 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.

Comparative Example 2 As a comparative example of Example 2, the same synthesis was performed without using an aromatic dicarboxylic acid, and the characteristics were evaluated. In a 1-liter separable flask equipped with a faucet connected to a reflux condenser with a 25 ml water content receiver, a thermometer and a stirrer, BAPP (2,2-bis [4- (4-aminophenoxy) phenyl] propane) 14.4 g (0.035 mol), 28.6 g of a reactive silicone oil X-22-161AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 408) as siloxane diamine ( 0.035 mol), TMA (trimellitic anhydride) 28.2 g (0.
147 mol), NMP (N-methyl-2-pyrrolidone)
245 g was charged and stirred at 80 ° C. for 30 minutes. Then, after adding 100 ml of toluene, the temperature was raised to about 160
Reflux at 2 ° C. for 2 hours. Approximately 2.5m of water in the water content receiver
After confirming that no more than 1 liter of water had flowed out, the temperature was increased to about 190 ° C. to remove toluene while removing the effluent accumulated in the water content determination receiver. Thereafter, the solution was returned to room temperature, the water content receiver was removed, and MDI was used as an aromatic diisocyanate.
(4,4-diphenylmethane diisocyanate) 20.
3 g (0.081 mol), triethylamine 2.1 g
(0.021 mol), and reacted at 110 ° 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.

Comparative Example 3 As a comparative example of Example 3, synthesis was performed without using an aromatic dicarboxylic acid, and the characteristics were compared. In a 1-liter separable flask equipped with a faucet connected to a reflux condenser with a 25 ml water content receiver, a thermometer and a stirrer, BAPP (2,2-bis [4- (4-aminophenoxy) phenyl] propane) 26.7 g (0.065 mol), 4.1 g of reactive silicone oil X-22-161AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 408) as siloxane diamine ( 0.005 mol),
28.2 g (0.147) of TMA (trimellitic anhydride)
Mol), NMP (N-methyl-2-pyrrolidone) 245
g and stirred at 80 ° C. for 30 minutes. Then, after adding 100 ml of toluene, the temperature is increased and about 160 ° C.
Refluxed for hours. Confirm that water has accumulated in the receiver for water determination at least about 2.5 ml, and that no outflow of water has been observed. The temperature was increased to remove the toluene. Thereafter, the solution was returned to room temperature, the water content measuring receiver was removed, and MDI (4,4-
20.3 g of diphenylmethane diisocyanate (0.
081 mol), 2.1 g of triethylamine (0.021
Mol), and reacted at 110 ° 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. Table 1 summarizes the composition.

[0033]

[Table 1] Item Siloxane diamine BAPP TMA Aromatic MDI TEA (mol) Dicarboxylic acid Example 1 0.07-0.147 0.07 0.161 0.021 Example 2 0.035 0.035 0.147 0.07 0.161 0.021 Example 3 0.005 0.065 0.147 0.07 0.161 0.021 Example 4 0.035 0.035 0.147 0.07 0.161- Comparative Example 1 0.07-0.147-0.081 0.021 Comparative Example 2 0.035 0.035 0.147-0.081 0.021 Comparative Example 3 0.005 0.065 0.147-0.081 0.021 Item Molecular weight (Mw) Modulus of elasticity 200 ° C (MPa) Modulus of elasticity 250 ° C (MPa) Example 1 75800 67 30 Example 2 52300 136 84 Example 3 78200 520 200 Example 4 47000 150 80 Comparative example 1 72000 21 1. 2 Comparative Example 2 69300 90 3.1 Comparative Example 3 54000 300 11

Examples 1 to 4 in Table 1 are siloxane-containing polyamideimides obtained in the present invention, and each of the siloxane-containing polyamideimides at 200 ° C. and 250 ° C. in comparison with Comparative Examples synthesized without using an aromatic dicarboxylic acid. At a high temperature. Further, the molecular weight when triethylamine was added as the basic catalyst in Example 2 was higher than that in Example 4 where triethylamine was not added in the same composition.

[0035]

The method for producing a polyamideimide according to the present invention, the polyamideimide obtained thereby and a varnish containing the same can be used for varnishes, adhesives and adhesive films which are required to have heat resistance. It can be widely used in the fields of wiring boards and electricity, the field of automobiles, the field of construction and building materials, and the like. And, compared to conventional resins, it has excellent heat resistance, drying properties, film moldability, and electrical properties, and because it is soluble in solvents, it does not require filtration or purification steps, and has a large molecular weight. A siloxane-containing polyamideimide can be produced industrially advantageously. Furthermore, it is possible to control physical properties such as elastic modulus and electrical properties while maintaining high film-forming properties depending on the siloxane content, the amount and type of aromatic dicarboxylic acid, and as a material with excellent mechanical properties especially at high temperatures. Can be used. Furthermore, when varnish is used as an interlayer insulating adhesive as a film,
The deterioration of mechanical properties due to heating is prevented, and the interlayer insulation resistance and connection reliability are improved.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J034 CA24 CB03 CB07 CC12 CC13 CC33 CC44 CC52 CC61 CC66 CD15 DM01 HA01 HA07 HC03 HC12 HC13 HC17 HC22 HC25 HC34 HC44 HC46 HC52 HC61 HC64 HC67 HC71 HC73 KB01 QA07 QC05 RA07 RA08 RA10 RA12 RA14 4J035 GA06 GB02 LA03 LB01 4J038 DJ051 GA15 JB03 KA04 KA06 NA21 PB09 PC02 4J043 PA04 PA08 PA19 QB32 RA06 RA35 SA06 SA11 SA85 TA12 TA21 UA121 UA122 UA131 UA132 UA141 UA151 UA261 UA26 XA UB05A UB12A 321 XA ZB01 ZB03 ZB11 ZB47

Claims (7)

[Claims] Claims 1. A diamine and trimellitic anhydride are reacted with each other in the presence of an aprotic polar solvent to form an amide acid, followed by dehydration and ring closure to produce a diimidedicarboxylic acid, which is reacted with a diisocyanate. A method for producing a polyamideimide, comprising reacting a diisocyanate with an aromatic dicarboxylic acid in the obtained polyamideimide. 2. The polyamideimide according to claim 1, wherein the diamine is at least a diamine containing a siloxane diamine represented by the general formula (1), and the diisocyanate is an aromatic diisocyanate represented by the general formula (2). Manufacturing method. Embedded image Embedded image 3. A mixture of (A) a siloxane diamine represented by the general formula (1) and (B) an aromatic diamine having three or more aromatic rings represented by the general formula (3) (A / B = 1
(0.00.0 / 0.0 to 0.1 / 99.9 mole ratio) and trimellitic anhydride to produce a diimidedicarboxylic acid, which is then reacted with an aromatic dicarboxylic acid represented by the general formula (4). A method for producing a polyamideimide, comprising coexisting and reacting with an aromatic diisocyanate represented by the general formula (2). Embedded image Embedded image 4. The process for producing a polyamideimide according to claim 1, wherein the reaction of the diimidedicarboxylic acid and the aromatic dicarboxylic acid with the diisocyanate is carried out in the presence of a basic catalyst. 5. The method for producing a polyamideimide according to claim 1, wherein a trialkylamine represented by the general formula (5) is used as the basic catalyst. Embedded image 6. A polyamideimide obtained by the production method according to claim 1. 7. A varnish containing a polyamideimide obtained by the production method according to claim 1.