JPS58101116A - Manufacture of polyamide-imide ester resin composition - Google Patents

Abstract

PURPOSE:To obtain titled novel composition soluble in cheap phenolic solvents, by the reaction, in an organic solvent, between a citric acid-contg. tricarboxylic acid and a diisocyanate followed by incorporating a polycarboxylic acid and a polyol and then carrying out a reaction. CONSTITUTION:A reaction is carried out in an oragnic solvent (pref. a mixture consisting of a phenolic solvent and an aromatic hydrocarbon one) between (A) 1mol of a tricarboxylic acid and/or its derivative containing >=5mol% of citric acid (pref, citric anhydride) (pref. trimellictic anhydride) and (B) 0.6-1mol of a diisocyanate and/or its derivative (pref. 2,4-tolylene diisocyanate) followed by incorporating (C) a polycarboxylic acid and/or its derivative and (D) a polyol to perform a reaction. EFFECT:Having good heat resistance and highly resistant to heta-shock.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field of the Invention) The present invention relates to a method for producing a novel polyamideimide ester resin composition.

(Prior art and its problems) Organic insulating materials used in electrical equipment vary depending on the form used, such as insulated wires, paints, films, laminates, impregnated resins, adhesives, etc., but include phenolic resins, polyvinyl formal resins, Polyester resins, alkyd resins, epoxy resins, polyesterimide resins, polyamideimide resins, polyimide resins, etc. are commonly used.

In recent years, due to the need to conserve resources and energy, and the miniaturization and weight reduction of peripheral equipment, the performance of electrical equipment itself has increased and the number of sheds has been increasing. The importance of organic materials is increasing.

In the field of insulating paints, it has replaced polyester resin paints, which have traditionally been widely used due to their relatively practical balance of heat resistance, mechanical properties, electrical properties, and economic efficiency.
In recent years, the use of imide group-containing resin coatings such as polyester, polyamide-imide, boria ζ-imide ester, and polyimide, which have improved heat resistance, has been increasing.

Among imide group-containing resins, polyamide-imide resin is known to have the best balance of heat resistance, mechanical properties, electrical properties, and chemical properties.

However, conventional aromatic polyamide-imide resins are compatible only with expensive organic polar solvents such as N-methyl-2-pyrrolidone and dimethylacetamide, which has the disadvantage of increasing the price of resin coatings.

Furthermore, since organic polar solvents have strong hygroscopic properties, it is difficult to control the storage and use of paints using these solvents.

In the field of insulated wires, we use polyamide-imide ester resin paint, which contains a considerable amount of ester component in polyamide-imide resin and dissolves in relatively inexpensive phenolic solvents such as phenol, cresol, and xylenol. However, compared to insulated wires using polyamide-imide resin paint, they have lower heat resistance and
It had the disadvantage of poor heat shock resistance.

(Object of the Invention) The object of the present invention is to produce a polyamide-imide ester composition that is soluble in an inexpensive phenolic solvent even when the amide-imide component is increased.

(Structure of the Invention) The present invention involves reacting a tricarboxylic acid containing at least 5 moles of citric acid with a diisocyanate in an organic solvent such as a phenolic solvent, and then adding a polycarboxylic acid and a polyol to react. t-%.

When a part of tricarboxylic acid is converted into citric acid and reacted,
Since the obtained polyamide-imide is dissolved in an inexpensive phenolic solvent, a polyamide-imide ester composition containing a large amount of amide-imide component and thus having improved heat resistance and heat shock properties can be obtained.

The citric acid used in the present invention can be used with or without water of crystallization, but from the viewpoint of reaction efficiency, since the reaction with diisocyanate and/or its derivatives is accompanied by dehydration. Preference is given to using anhydrous citric acid without water of crystallization.

Excluding citric acid, tricarboxylic acids and/or derivatives thereof include, for example, aromatic tricarboxylic acids, aromatic tricarboxylic acid esters, aromatic tricarboxylic acid anhydrides, and the like represented by formulas (1) and (1), used alone or in mixtures. It will be done.

Generally, trimellitic anhydride is preferred from the viewpoints of heat resistance, high reactivity, drug resistance, etc.

In addition, in order to increase the imide bond ratio and improve heat resistance, part of the tricarboxylic acid was replaced with romellitic anhydride, 3, 3',
It is also possible to substitute 4,4'benzophenonetetracarboxylic acid anhydride, a tetracarboxylic acid such as butanetetracarboxylic acid, or a derivative thereof.

On the other hand, if you want to increase the number of amide bonds from the para/para aspect of the properties of a multicomponent system, use terephthalic acid, isophthalic acid,
Aromatic or aliphatic, basic acids such as tricarboxylic acid, malonic acid, co-phosphoric acid, glutaric acid, ajibi/acid, pimelic acid, speric acid, azelaic acid, etc. can also be used as part of the tricarboxylic acid. The proportion of citric acid in the tricarboxylic acid and/or its derivative must be 5 moles or more from the viewpoint of solubility in organic solvents.

If the amount is less than 5 molti, the solubility in organic solvents, especially phenolic solvents will decrease, making it impossible to obtain a practical resin composition.

The higher the ratio of citric acid, the higher the solubility in organic solvents.The ratio of citric acid can be arbitrarily changed within the above range depending on the form in which the resin composition of the present invention is used.

As the diisocyanate and/or its derivative used in the present invention, any aliphatic, alicyclic, or aromatic diisocyanate and/or its derivative can be used. Suitable diisocyanates include ethylene diisocyanate, rimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, trimethylhexamethylene diisocyanate,
Morpholine diisocyanate, cyclohexane diisocyanate, 3,9-bis(pyropyl 3-isocyanate), 2,4@8,10-nato2oxaspiro [5.5]
Aliphatic and alicyclic diincyanates such as undecane, 4
・4'-diphenylmethane diisocyanate, 4.4'
-diphenylpropane diisocyanate, 4,4'-diphenylsulfone diisocyanate, 3,3'-diphenylsulfone diisocyanate $-), 4,4'-diphenylsulfite diisocyanate, 3,3'-dimethyl-
4,4'-diphenylmethane diincyanate, 3,3
'-dichloro-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4-4'-bisphenyl diincyanate, 3,3'-dimethoxy-4,4'-
bisphenyl diisocyanate), 4@4'-bisphenyl diisocyanate), m-phenylene diisocyanate, P-phenylene diisocyanate), 2@4-) lylene diisocyanate, 2,6-tolylene diisocyanate, m There are aromatic diisocyanates such as -xylylene diisocyanate and P-xylylene diisocyanate, which can be used alone or in combination.

Further, diisocyanate derivatives in which the incyanate group of diisocyanate is masked with phenol, cresol, xylenol, etc. can also be used.

- of diisocyanate or/and its derivatives.

Part f: 4,4',4''-triisocyanate-triphenylmethane 2@2',5,5'-tetraisocyanate-4,4'-dimethyldiphenylmethane, etc. may be replaced with trivalent or higher polyisocyanate. can.

Among the incyanate compounds, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diinocyanate,
2,6-tolylene diisocyanate, m-xylylene diisocyanate), P-xylylene diisocyanate, 4
- It is preferable to use 4'-diphenyl ether diisocyanate alone or in combination.

Examples of organic solvents used in the present invention include phenol, 0-
Cresol, m-cresol, P-cresol, various xylenolic acids, various chlorophenols, nitrobenzene, N-methyl-2-pyrrolidone, N@N' dimethylformamide, N.■ dimethylacetamide, hexamethylphosphoramide, Examples of solvents that can be used in combination with these include veneer/in, toluene, xylene, and aromatic hydrocarbons with high boiling points (e.g., Maruzen Sekiyu Swazol 1000, Swazol 1500, Nippon Oil's Nippon Oil Hysol 100.8). stone hysol iso
etc.), ethylene glycol monomethyl ether acetate, etc.

Special KIFf'! The new solvent composition is based on the stability of the resulting resin solution, film forming properties, economic efficiency, etc., and phenol, cresol,
It is a mixture of a 7-enol solvent such as xylenol and a high boiling point aromatic hydrocarbon solvent.

There is no particular limit to the solid content concentration during the reaction, but if it is less than 35, the reaction will take a long time, side reactions will easily occur, and a highly polymerized resin composition will not be obtained, so it should be at least SSS. I really like it.

The reaction of the present invention can be accelerated by catalysts commonly used for reactions of isocyanates.

Examples of suitable catalysts include - lead oxide, boric acid, lead naphthenate, metal salts of heptanoic acids such as zinc, phosphoric acid, polyphosphoric acid, organic titaniums such as dibutyl titanate, triethanol achin titanate, etc. metal compound, triethylamine, 1
@8-diaza-bicyclo(5,4,0)lindecene-7
(including this acid adduct), etc.

A suitable amount to be used is 0.01 to 5-5% per solid content at the time of preparation, and the method of addition is not limited to %.

Polycarboxylic acids and/or derivatives thereof used in the present invention include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and derivatives thereof, 3,3',4,4'-benzophenonetetracarboxylic anhydride, butanetetra Examples include tetracarboxylic acids such as carboxylic acids.

Examples of the polyol used in the present invention include ethylene glycol, propylene glycol, glycerin, trihydroxyethyl isocyanurate, and the like.

In the present invention, 1.0 mol of a tricarboxylic acid and/or its derivative containing citric acid as an essential component and 0.6 to 1.0 mol of a diisocyanate and/or its derivative are simultaneously added to an organic solvent. Alternatively, one can be dissolved in a solvent and the other can be added at once or in several batches, and there are no restrictions on the method of addition.

The reaction is controlled to the extent of bubbling of generated carbon dioxide and distillation of reaction water, and K is controlled within an appropriate range by observing the viscosity of the solution.
Generally, the reaction temperature is 60 to 350°C, preferably 70 to 350°C.
The reaction is carried out at 250° C. for several hours to several tens of hours. Subsequently, polycarboxylic acid and polyol are added to the reaction solution in an appropriate ratio, and the reaction mixture is heated and esterified using a conventional method. The amount of polycarboxylic acid or polyol to be added is appropriately selected depending on the preferred ratio of amide-imide content and ester content.

(Effect of invention q) The resin composition of the present invention thus obtained exhibits extremely excellent solubility even in phenolic solvents due to the use of tricarboxylic acid and/or derivatives thereof having citric acid as an essential component, and It has superior heat resistance than conventional polyamide-imide ester resins, which have a high ester content and are soluble in phenolic solvents.Also, the ratio of amide-imide to ester can be changed arbitrarily, and it can be used as an impregnated resin in addition to insulation paints. ,
It is extremely useful in practical applications, as it can be applied not only to electrical insulation materials such as stacking boards, films, and adhesives, but also to heat-resistant paints, fibers, and molded resins.

(Example of the invention) The present invention will be explained below with reference to Examples.

Example 1 Anhydrous citric acid 19.2F (0°1 mole) was placed in a 93T4 tube flask equipped with a thermometer, stirrer, cooling tube, and nitrogen inlet tube.
trimellitic anhydride 1728 F (0.9 mol),
diphenylmethane diinocyane) 250.3f (1,
0 mol), m-cresol (30 Of'l) was charged, and the temperature was raised to 200°C over about 1 hour in a nitrogen stream.

Significant foaming was observed from around 70°C, and further foaming and distilled water were observed from 160 to 180°C. React at this temperature for 2 hours, and then add 33.2F (0.2 mol) of terephthalic acid.
Ethylene glycol 14.9 F (0.24 mol) and glycerin 3.7 t (0.04 mol) were added, and the reaction was continued for an additional 4 hours at 210° C. while distilling out cresol. When the remaining amount of cresol drips out is 150 t, the viscosity increases and it approaches the gel point, add a mixed solvent of cresol/naphtha = 7/3, and stir thoroughly to remove the non-volatile content (200 cxtsn).
) 30, 1-1 A reddish-brown transparent resin solvent with viscosity (25° C.) and 61 voids was obtained.

The obtained resin solution ti, o is placed on the steel wire at a furnace temperature of 4 G.
Table 1 shows the properties of the insulated wire obtained by coating and baking at G° C. and a line speed of 10 ml/min.

Example 2 34170 with thermometer, stirrer, cooling tube and nitrogen inlet tube
38.4 t (0.2 mol) of anhydrous citric acid in 7 lasco
, trimellitic anhydride 153.7 F (0.8 mol), diphenylmethane diisocyanate 250.3 F (
1.0 mol) and cresol 2509, and heated to 200 'C' in a nitrogen stream for about 2 hours! The temperature was raised with

Around 70'C, significant foaming occurs at 160-200'C.
When K was applied, foaming and distilled water were observed at the same time. At this temperature 2
49.8 t (0.3 t) of terephthalic acid
mol), trihydroxyethyl isocyanurate) (T
HEIC) 52 f (0,2 mol) added to 210
The reaction was allowed to proceed at ℃ for 4 hours while distilling the cresol. When the viscosity increases and approaches the gel point, cresol/
A mixed solvent of 7s = 8/z was added and thoroughly stirred to obtain a reddish-brown transparent resin solution with a non-volatile content of 35-1 and a viscosity of 72 poise (25°C).

The obtained resin solution was placed on a 1.0 inch width copper wire at a furnace temperature of 400℃.
Table 1 shows the properties of the insulated wire obtained by coating and baking at a temperature of 1 Gm/min at a wire speed of 1 Gm/min.

Example 3 A thermometer stirrer, a cooling tube, and a nitrogen introduction tube were attached (93 mol),
Diphenylmethane diisocyanate 200.2F (0,
8 mol), m-cresol, and 250 ft of m-cresol were charged, and the temperature was raised to 200° C. over about 1 hour in a nitrogen stream.

Significant foaming was observed from around 70°C, and a slight amount of distilled water was observed from 160 to 170°C. After reacting at this temperature for 2 hours, terephthalic acid 33.2 F (0.2 mol), ethylene glycol 14.9 F (0.24 mol), trihydroxyethyl inocyanurate) 26 F (0.1 mol)
was added and reacted at 210° C. for 4 hours while distilling cresol. When the viscosity increases and approaches the gelling point, add a mixed solvent of cresol/su7su = 8/2 and stir thoroughly to obtain a solution with non-volatile content (200°C x 1.5H) of 30% and viscosity (25°C) of 44%. A reddish-brown transparent resin solvent of Boyes was obtained.

Table 1 shows the properties of the insulated wire obtained by coating and baking the obtained resin solution onto a steel wire having a width of t1.0 in the same manner as in the example.

Table 1 below (insulated wire test #1 conducted in accordance with JI8 C3003).

(Note) Polyester amide-imide paint manufactured by Westinghouse, trade name Omega.

Claims (1)

[Scope of Claims] 1. 1.0 mol of a tricarboxylic acid and/or its derivative containing at least 5 mol of citric acid and 0.6 to 1.0 mol of a diisocyanate and/or its derivative in an organic 1. A method for producing a polyamide-imide ester resin composition, characterized in that after reacting in a solvent, polycarboxylic acid and/or its derivatives are added and reacted with a polyol. 2. Claim 1 in which the tricarboxylic acid other than citric acid and/or its derivative is trimellitic anhydride
A method for producing a polyamideimide ester resin composition as described in Section 1. 6. The method for producing a polycarboxylated toimide ester resin composition according to claim 1 or 2, wherein the polycarboxylic acid is an aromatic dicarboxylic acid.