JP2996638B2 - Polyamide imide resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyamideimide resin which is very useful for applications such as films, electric wire coatings, adhesives, paints, and laminates used at high temperatures.

[0002]

2. Description of the Related Art Polyimide resins and polyamide resins are used in very many fields, taking advantage of excellent properties such as heat resistance. On the other hand, development of polyamide imide resin, polyester imide resin, polyether imide resin and the like has been widely promoted in order to expand their versatility while utilizing these characteristics.

[0003]

However, polyimide resins, polyamide resins, polyamide-imide resins, etc., which are currently widely used, have good heat resistance, but have drawbacks in moldability and the like. Therefore, in order to balance these advantages and disadvantages, the formation of a composite of another reactive resin or the like with a polyimide resin, a polyamide resin, a polyamidoimide resin, or the like has been studied, but the situation is still insufficient. The main obstacle is that the solvent solubility of these polyimide resins, polyamide resins and polyamide-imide resins is insufficient, and that these polyimide resins, polyamide resins, polyamide-imide resins and other reactive resins have a desired composition. And that the desired characteristics were not exhibited. Accordingly, an object of the present invention is to provide a polyamide-imide resin that is soluble in an organic solvent, has a reactive active site for another reactive resin, and can be complexed with another reactive resin.

[0004]

The present invention provides a compound represented by the general formula (I):

Embedded image [Wherein Ar is a divalent aromatic group, and R ¹ is

Embedded image (Where Z is a direct bond, O, C = O, CH ₂ , S, SO
Or SO ₂ , and R ⁴ and R ⁵ are a hydrogen atom, methyl
Group, halogen atom, nitrile group, hydroxyl group
You. ) , R ² and R ³ are divalent aliphatic or alicyclic divalent groups different from R ¹ , l, m, n, x and y are 1 ≧
2 (m + n), x ≧ 2y, 1 ≦ 5, and x ≦ 6, which are positive integers]. Substituents Ar, R ¹ , R
Examples of the divalent aliphatic group for R ² and R ³ include a phenylene group and Ph
_{-O-Ph, Ph-SO 2} -Ph, (Ph is a phenylene group) and the like are preferable.

The polyamide-imide resin of the present invention is obtained by polycondensation reaction of a dicarboxylic acid component containing an imidodicarboxylic acid of the following general formula (IV) with another diamine component containing a diamine of the general formula (III).

Embedded image (Where Z is a direct bond, O, CＣO, CH ₂ , S, S0
Or SO ₂ , wherein R ⁴ and R ⁵ are a hydrogen atom, a methyl group,
It means a halogen atom, a nitrile group or a hydroxyl group. )

Embedded image (The symbols in the formula have the above-mentioned meanings)

[0006] Examples of the diamine of the general formula (III) include the following compounds. N, N'-bis [4- (4-aminophenoxy) phenyl] -5-hydroxyisophthalamide, N, N'-bis [4- (4-
Aminophenylsulfinyl) phenyl] -5-hydroxyisophthalamide, N, N'-bis [4- (4-aminophenylsulfenyl) phenyl] -5-hydroxyisophthalamide, N, N'-bis [4- (4 -Aminophenylsulfonyl) phenyl] -5-hydroxyisophthalamide, N, N'-bis [4- (4-aminophenyl) phenyl) -5-hydroxyisophthalamide, N, N'-bis [4- (4- Aminobenzoyl) phenyl] -5-hydroxyisophthalamide, N, N '
-Bis [4- (4-aminobenzyl) phenyl] -5
Hydroxyisophthalamide, N, N'-bis [3-
(3-aminophenoxy) phenyl] -5-hydroxyisophthalamide, N, N'-bis [3- (3-aminophenylsulfinyl) phenyl] -5-hydroxyisophthalamide, N, N'-bis [3- ( 3-aminophenylsulfenyl) phenyl] -5-hydroxyisophthalamide, N, N'-bis [3- (3-aminophenylsulfonyl) phenyl] -5-hydroxyisophthalamide, N, N'-bis [3- (3-aminophenyl) phenyl] -5-hydroxyisophthalamide,
N, N'-bis [3- (3-aminobenzoyl) phenyl] -5-hydroxyisophthalamide, N, N'-bis [3- (3-aminobenzyl) phenyl] -5-hydroxyisophthalamide, N'-bis (4- (4-
Aminophenoxy) phenyl] -4-hydroxyisophthalamide, N, N′-bis [4- (4-aminophenylsulfinyl) phenyl] -4-hydroxyisophthalamide, N, N′-bis [4- (4-amino Phenylsulfenyl) phenyl] -4-hydroxyisophthalamide, N, N'-bis [4- (4-aminophenylsulfonyl) phenyl) -4-hydroxyisophthalamide, N, N'-bis [4- (4-amino Phenyl) phenyl] -4-hydroxyisophthalamide, N, N'-bis [4- (4-aminobenzoyl) phenyl] -4-
Hydroxyisophthalamide, N, N'-bis [4-
(4-aminobenzyl) phenyl] -4-hydroxyisophthalamide, N, N'-bis [4- (4-aminophenoxy) phenyl) -2-hydroxyterephthalamide, N, N'-bis [4- (4 -Aminophenylsulfinyl) phenyl] -2-hydroxyterephthalamide, N, N'-bis [4- (4-aminophenylsulfenyl) phenyl] -2-hydroxyterephthalamide, N, N'bis [4- (4 -Aminophenylsulfonyl) phenyl] -2-hydroxyterephthalamide,
N, N'-bis [4- (4-aminophenyl) phenyl] -2-hydroxyterephthalamide, N, N'-bis [4- (4-aminobenzoyl) phenyl] -2-hydroxyterephthalamide, N'bis [4- (4-
Aminobenzyl) phenyl] -2-hydroxyterephthalamide and the like.

The polyamideimide resin of the present invention is prepared by synthesizing an imidodicarboxylic acid represented by the general formula (IV) from, for example, trimellitic anhydride and a diamine of the general formula (III) by a known imidation reaction. (I
V) can be prepared by reacting V) with a diamine of the general formula (III). If necessary, an amide-forming derivative such as an alkyl ester, an aryl ester, or an acid halide of the imide dicarboxylic acid may be used in place of the imide dicarboxylic acid of the general formula (IV), and the diamine of the general formula (III) may be used instead of the diamine. Amide-forming derivatives such as N, N'-diacyldiamino derivatives may be used.

In order to synthesize the polyamide-imide resin of the present invention, polycondensation is performed with a diamine of the general formula (III) and another diamine. Examples of other diamines include the following compounds. N, N'-bis (2-aminophenyl) isophthalamide, N, N'-bis (3-aminophenyl) isophthalamide, N, N'-bis (4-
Aminophenyl) isophthalamide, N, N'-bis (2-aminophenyl) terephthalamide, N, N'-
Bis (3-aminophenyl) terephthalamide, N,
N'-bis (4-aminophenyl) terephthalamide,
N, N'-bis (2-aminophenyl) phthalamide,
N, N'-bis (3-aminophenyl) phthalamide,
N, N'-bis (4-aminophenyl) phthalamide,
N, N'-bis (2-aminophenyl) phthalamide,
N, N'-bis (3-aminophenyl) phthalamide,
N, N'-bis (4-aminophenyl) phthalamide,
N, N'-bis (4-amino-3,5-dimethylphenyl) isophthalamide, N, N'-bis (4-amino-
3,5-dimethylphenyl) terephthalamide, N,
N'-bis (4-amino-3,5-dimethylphenyl) phthalamide, N, N'-bis (4-amino-3,
5-dimethylphenyl) phthalamide, N, N'-bis (4-amino-n-butyl) diisophthalamide,
N, N'-bis (4-amino-n-hexyl) isophthalamide, N, N'-bis (4-amino-n-dodecyl) isophthalamide, m-phenylenediamine, p-
Phenylenediamine, metatolylenediamine, 4,4
'-Diaminodiphenyl ether, 3,3'dimethyl-4,4'-diaminodiphenyl ether, 3,3 '
-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminophenylthioether, 3,3'-dimethyl-4,4'-diaminophenylthioether, 3,3'-diethoxy-4,
4'-diaminodiphenylthioether, 3,3'-
Diaminodiphenylthioether, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-
Diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
3,3'-dimethoxy-4,4'diaminodiphenylmethane, 2,2'-bis (4-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, 4,4'-diaminodiphenylsulfoxide ,
4,4'-diaminodiphenylsulfone, 3,3'-
Diaminodiphenyl sulfone, benzidine, 3,3 '
-Dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-diaminobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane,
2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-chloro-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [ 3,5-dimethyl-4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane,
1,1-bis [3-chloro-4- (4-aminophenoxy) phenyl] ethane, bis [4- (4-aminophenoxy) phenyl] methane, bis [3-methyl-4- (4
-Aminophenoxy) phenyl] methane, piperazine,
Hexamethylenediamine, heptamethylenediamine, tetramethylenediamine, p-xylenediamine, m-xylenediamine, 3-methylheptamethylenediamine and the like.

100 mol% of a diamine of the general formula (III)
On the other hand, the other diamine is 50 mol% or less, particularly 30 mol%.
It is preferable to set the following. In the method for producing a polyamide-imide resin of the present invention, the imide of the general formula (IV) may be used, if necessary, in the polycondensation reaction of the imide dicarboxylic acid component of the general formula (IV) and the diamine of the general formula (III). Some of the dicarboxylic acids and / or their amide-forming derivatives may be used in combination with other dicarboxylic acids and / or their amide-forming derivatives other than those constituting the general formula (IV). When synthesizing the imidodicarboxylic acid component, a part of the diamine of the general formula (III) may be used in combination with another diamine. Other dicarboxylic acids other than those constituting the general formula (IV) include succinic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, 1 , 3-cyclohexanedicarboxylic acid, isophthalic acid, 4,4'-biphenyldicarboxylic acid,
3,3'-methylene dibenzoic acid, 4,4'-methylene dibenzoic acid, 4,4'-oxybenzoic acid, 4,4'-
Thiodibenzoic acid, 3,3'-carbonyldibenzoic acid,
4,4'-carbonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid, 1,4-naphthalenedicarboxylic acid,
1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane and the like can be mentioned.

The imidodicarboxylic acid of the general formula (IV) used in the present invention can be easily produced by a known imidization reaction. That is, inactive substances such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, and hexamethylphosphoric triamide. In a polar organic solvent, the diamine is blended in an amount of 0.4 to 0.6 equivalent to 1 equivalent of trimellitic anhydride, and -20 to 3 is added.
It is preferable to produce the amic acid by reacting it at a temperature in the range of 100 ° C., preferably in the range of 0 to 60 ° C. for a sufficient time to several days, and further imidize it.

Examples of the imidation method include a method of dehydrating a ring by heating and a method of chemically closing a ring using a dehydration catalyst. In the case of ring closure by dehydration by heating, the reaction temperature is 150 to 400 ° C, preferably 180 to 35 ° C.
0 ° C. and the time is 30 seconds to 10 hours, preferably 5 minutes to 5 hours. When a dehydration ring-closing catalyst is used, the reaction temperature is 0 to 180 ° C, preferably 10 to 180 ° C.
80 ° C., and the reaction time ranges from tens of minutes to several days, preferably from 2 hours to 12 hours. Acid anhydrides such as acetic acid, propionic acid, butyric acid, and benzoic acid are used as the dehydration ring-closing catalyst, and it is preferable to use pyridine and the like in combination as a compound that promotes the cyclization reaction. The amount of the dehydration ring-closing catalyst used is 200 mol% or more, preferably 300 to 1000 mol%, based on the total amount of the diamine. In addition, the amount of the compound that promotes the chemical reaction is 150 to the total amount of the diamine.
~ 500 mol% is preferred.

Polycondensation reaction of a dicarboxylic acid component having an imide dicarboxylic acid of the general formula (IV) as a main component and a diamine component having a diamine of the general formula (III) as a main component for forming the polyamideimide resin of the present invention. It is preferable to mix 1 equivalent of the diamine component with respect to 1 equivalent of the carboxylic acid component, add a condensing agent, and perform the reaction in a solvent. As the solvent, toluene, benzene, chlorobenzene, dichlorobenzene, acetonitrile, pyridine, tetrahydrofuran, acetic anhydride, dichloromethane, hexane, cyclohexane, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide Are used. If necessary, inorganic salts typified by lithium chloride and calcium chloride can be added to the reaction system to increase the solvating power of the protic solvent and to suppress side reactions.

As the condensing agent, triphenyl phosphite,
Diphenyl phosphite, tri-o-tolyl phosphite, di-o-tolyl phosphite, tri-m-tolyl phosphite, di-m-tolyl phosphite, tri-p-tolyl phosphite, Di-p-tolyl phosphite, di-o-chlorophenyl phosphite, tri-p-chlorophenyl phosphite, di-p-chlorophenyl phosphite, dicyclohexylcarbodiimide, triphenyl phosphate, diphenyl phosphonate and the like are used. . The reaction temperature is preferably in the range of 60 to 150C. The reaction is usually completed in a few minutes to 24 hours. In some cases, the reaction solution is heated to a high temperature, or
The reaction conditions may be such that the generated water is removed to shift the equilibrium to the production system. The resulting polyamideimide resin has an intrinsic viscosity (0.5 g / dl in N-methyl-2-pyrrolidone).
(Concentration, 30 ° C.) is 0.1 to 0.5 dl / g, preferably 0.2 to 1.5 dl / g.

[0014]

【Example】

Example 1 N, N'-bis [4- (4-aminophenoxy) phenyl] -5-hydroxyisophthalamide 21.8 g
(40 mmol) and 1.1 g of m-phenylenediamine
(10 mmol) and 32 g of trimellitic anhydride (100
(Mmol) was dissolved in 150 ml of N-methyl-2-pyrrolidone and reacted at room temperature under a nitrogen atmosphere for 6 hours to obtain a polyamic acid solution. This polyamic acid solution was added to 20
The mixture was heated at 0 ° C. for 2 hours to carry out a dehydration cyclization reaction. After cooling, 27.3 g (50 mmol) of N, N-bis [4- (4-aminophenoxy) phenyl) -5-hydroxyisophthalamide, 25 ml of pyridine,
31 g (100 mmol) of triphenyl phosphite and 5 g (125 mmol) of lithium chloride were added sequentially,
For 6 hours. After cooling, the polymer solution was poured into a large amount of methanol. The precipitated solid was separated by filtration, and the filtrate was washed with hot methanol and dried, and had an intrinsic viscosity of 0.4.
7 dl / g (0.5 g in N-methyl-2-pyrrolidone
/ Dl concentration, 30 ° C).

Example 2 27.3 g of N, N'-bis [4- (4-aminophenoxy) phenyl] -5-hydroxyisophthalamide (5
0 mmol) and 32 g (100 mmol) of trimellitic anhydride were dissolved in 150 ml of N-methyl-2-pyrrolidone and reacted under a nitrogen atmosphere at room temperature for 6 hours to obtain a polyamic acid solution. This polyamic acid solution is heated to 200 ° C.
For 2 hours to carry out a dehydration cyclization reaction. After cooling, 1.7 g (10 mmol) of isophthalic acid and N, N'-bis [4- (4-aminophenoxy) were added to the reaction mixture.
Phenyl] -5-hydroxyisophthalamide 32.7
g (60 mmol), pyridine 30 ml, triphenyl phosphite 37.2 g (120 mmol), and lithium chloride 6 g (150 mmol) were sequentially added, and the mixture was stirred at 100 ° C. for 6 hours. After cooling, the polymer solution was poured into a large amount of methanol. The precipitated solid is separated by filtration, and the filtrate is washed with hot methanol and dried, and has an intrinsic viscosity of 0.50 dl.
/ G (0.5 g / dl in N-methyl-2-pyrrolidone)
(Concentration, 30 ° C.).

Example 3 27.3 g of N, N'-bis [4- (4-aminophenoxy) phenyl] -5-hydroxyisophthalamide (5
0 mmol) and 32 g (100 mmol) of trimellitic anhydride were dissolved in 150 ml of N-methyl-2-pyrrolidone and reacted under a nitrogen atmosphere at room temperature for 6 hours to obtain a polyamic acid solution. This polyamic acid solution is heated to 200 ° C.
For 2 hours to carry out a dehydration cyclization reaction. After cooling, 21.8 g (40 mmol) of N, N'-bis [4- (4-aminophenoxy) phenyl] -5-hydroxyisophthalamide and 1.1 g (10 mmol) of m-phenylenediamine were added to the reaction mixture. ), 25 ml of pyridine, 31 g (100 mmol) of triphenyl phosphite and 5 g (125 mmol) of lithium chloride were sequentially added, and the mixture was stirred at 100 ° C for 6 hours. After cooling, the polymer solution was poured into a large amount of methanol. The precipitated solid is separated by filtration, and the filtrate is washed with hot methanol and dried, and has an intrinsic viscosity of 0.50 dl.
/ G (0.5 g / dl in N-methyl-2-pyrrolidone)
(Concentration, 30 ° C.).

It was confirmed that the polyamide-imide resins obtained in Examples 1 to 3 had the following repeating units. Example 1

Embedded image Example 2

Embedded image Example 3

Embedded image

[0018]

The polyamide-imide resin obtained by the present invention is excellent in heat resistance and solvent solubility, and can be compounded with other reactive resins. The polyamide-imide resin of the present invention is useful as a material used at high temperatures for films, wire coatings, adhesives, paints, laminates and the like.

Claims (1)

(57) [Claims] 1. A compound of the general formula (I) Wherein Ar is a divalent aromatic group, and R ¹ is (Where Z is a direct bond, O, C = O, CH ₂ , S, SO
Or SO ₂ , and R ⁴ and R ⁵ are a hydrogen atom, methyl
Group, halogen atom, nitrile group, hydroxyl group
You. ) , R ² and R ³ are divalent aliphatic or alicyclic divalent groups different from R ¹ , l, m, n, x and y are 1 ≧
2 (m + n), x ≧ 2y, a positive integer of 1 ≦ 5, x ≦ 6]].