JPS58101117A - Polyamide-imide resin composition and its manufacture - Google Patents

Abstract

PURPOSE:To obtain titled composition of outstanding heat resistance and solubility in organic solvents, by incorporating a masked polyisocyanate in a reaction product derived from a citric acid-contg. polycarboxylic acid and a diisocyanate followed by carrying out a reaction. CONSTITUTION:A masked polyisocyanate (e.g. a compound prepared by masking with a phenol an aromatic diisocyanate, its dimer etc.) is incorporated at <=140 deg.C in a product prepared by dissolving in a solvent (e.g. phenol) (A) a citric acid (pref. citric anhydride)-contg. polycarboxylic acid and/or its derivative[e.g. composed of 5mol% of citric acid and the rest of an aromatic tricarboxylic acid (derivative)]and (B) a diisocyanate and/or its derivative (e.g., 4,4'-diphenylmethane diisocyanate) and then carrying out, in the presence of a catalyst (e.g. lead monoxide), a reaction at 60-350 deg.C for ca, several tens hours followed by a reaction to obtain the objective composition. USE:For electrical insulating coatings, impregnating resins, laminates, films, adhesives, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel polyamideimide resin composition and a method for producing the same.

Organic insulating materials (used in electrical equipment) include phenol resins, polyvinyl formal resins, polyester resins, alkyd resins, epoxy resins,
Polyesterimide resin, polyamide resin, polyimide resin, etc. are commonly used.

In recent years, due to the need for resource and energy conservation and the miniaturization and weight reduction of peripheral equipment, the high performance and miniaturization of electrical equipment itself has been progressing. The importance of organic materials is increasing.

In the field of insulating materials, 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balance of heat resistance, mechanical properties, electrical properties, and economic efficiency, have recently been replaced by paints with improved heat resistance. The use of imide group-containing resin coatings such as polyesterimide, polyamideimide, and polyimide is 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 only soluble in 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 are highly hygroscopic, paints using them as solvents also have the disadvantage of being difficult to manage during storage and use.

For this reason, in the field of insulated wires that use insulating paint, there are insulated wires and polyester resins that use polyesterimide resin paints that are soluble in relatively inexpensive phenolic solvents such as phenol, cresol, and quinlenol, at the expense of heat resistance. , double-coated wires with polyester-imide resin paint on the bottom layer and polyamide-imide resin paint on the top layer and baked have come to be mainly used, but insulated wires using polyamide-imide resin paint have a good balance of characteristics. Because of this lack of quality, it has not been possible to meet the harsh demands of current electrical equipment.

Therefore, many proposals have been made for polyamide-imide resins that are partially aliphatic-modified and have excellent solubility in organic solvents by using amino acids, lactams, etc. as raw materials (for example, Japanese Patent Publication No. 56-17374, Japanese Patent Publication No. 56-17374, 2
2330, Special Publication No. 56-34210).

However, when aliphatic modification is performed in which methylene chains are introduced into the molecule, as is the case with lactam, the heat resistance, especially the heat softening temperature when used as an insulated wire, is inferior to that of aromatic polyamide-imide resins. It had some drawbacks.

The present inventor conducted intensive research to develop a polyamide-imide resin composition that has excellent solubility and contains a large amount of imide components. A polyamide resin that is used as part of the polyhydric carboxylic acid component and reacted with diisocyanate, which has superior heat resistance than conventional aromatic polyamide-imide resins, and also has significantly improved solubility in organic solvents. It was proposed earlier that a composition could be obtained.

However, the previously proposed polyamide-imide resin had the disadvantage that when attempting to obtain an insulated wire using a recent high-speed, high-efficiency baking machine, the baking process becomes relatively narrow.

In other words, baking at high wire speeds deteriorates the flexibility of the insulating coating, while lower wire speeds reduce production efficiency, while oxidation of the copper wire surface reduces adhesion. Ta.

By adding a masked polyisocyanate compound to the proposed polyamide-imide resin composition, flexibility,
It has been found that the adhesion is greatly improved and therefore a wide range of printing operations can be obtained.

It has also been found that the heat resistance of the insulated wire, particularly the heat softening temperature, is greatly improved.

The present invention was made based on this knowledge, and is characterized by adding a masked polyisocyanate compound to a reaction product of a polycarboxylic acid containing citric acid and/or a derivative thereof and a diisocyanate and/or a derivative thereof. The present invention aims to provide a polyamide-imide resin composition and a method for producing the same.

The citric acid used in the present invention can be used with or without water of crystallization, but since the reaction with diisocyanate and/or its derivatives involves dehydration, the reaction rate is low. From this point of view, it is preferable to use anhydrous citric acid that does not contain water of crystallization.

Examples of tricarboxylic acids other than citric acid and/or derivatives thereof include aromatic tricarboxylic acids, aromatic tricarboxylic acid esters, aromatic tricarboxylic acid anhydrides, etc. shown in (1) and (II) alone or in combination of two or more. It is used as

Generally, trimellitic anhydride is preferred due to its heat resistance, high reactivity, economical efficiency, etc.

Aromatic, alicyclic, or aliphatic tetracarboxylic acids or derivatives thereof can be used in combination with tricarboxylic acids and/or derivatives thereof including citric anhydride.

Examples of such tetracarboxylic acids include pyromellitic acid, 3.3',4.4'-benzophenonetetracarboxylic acid, butanetetracarboxylic acid, 3°3',4,
4'-diphenyltetracarboxylic acid, 2.2'.

3.3'-diphenyltetracarboxylic acid, Vinclo (2
,2,2)-oct-(7)-ene-2:3.5:6-
Tetracarboxylic acid, 3,3',4,4'-diphenyl ether tetracarphonic acid, 2.2'1313'
-diphenyl ethertetracarboxylic acid, 1.4.5゜8-naphthalenetetracarboxylic acid, 2.3,6.7-naphthalenetetracarboxylic acid, 1.2.5.6 -naphthalenetetracarboxylic acid, 2.2- Bis-(3゜4-dicarboxyphenyl)sulfone, 2.5-bis(3,4
-dicarboxyphenyl) 1,3,4-oxydiazole or derivatives thereof such as anhydrides and esters thereof.

Among these, pyromellitic anhydride, 3.3', 4゜4
'-Penzophenonetethocarboxylic anhydride, butanetetracarboxylic acid, and 3,3',4,4'-diphenyltetracarboxylic anhydride have excellent heat resistance, solubility, and economic efficiency and are suitable for the present invention. ing.

Examples of dicarboxylic acids and/or derivatives thereof that can be used in combination with tricarboxylic acids and/or derivatives thereof including citric anhydride include terephthalic acid, isophthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, and adipine. Examples include aromatic or aliphatic dibasic acids such as pimelic acid, speric acid, and azelaic acid, and derivatives such as esterified products thereof.

In view of the balance between solubility in organic solvents and heat resistance, it is desirable that the ratio of citric acid in tricarboxylic acid and/or its derivatives be 5 mol% or more, and when it is desired to increase the imide bond ratio and particularly increase heat resistance. It is desirable to use 10 mol% to 90 mol% of tricarboxylic acid and/or its derivatives containing citric acid and 90 mol% to 10 mol% of tetracarboxylic acid and/or its derivatives.

On the other hand, if you want to improve the mechanical properties such as flexibility and adhesion of the insulated wire coating while maintaining heat resistance, use 90 mol% to 10 mol% of dicarboxylic acid instead of tetracarboxylic acid and/or its derivatives. It is preferable to use

If citric acid is less than 5 mol% in tricarboxylic acid and/or its derivative, or tricarboxylic acid and/or its derivative is less than 10 mol% in the acid component, the organic solvent of the polyamide-imide resin composition, especially The solubility in phenolic solvents decreases, making it difficult to obtain a practical resin composition1.Also, if the tetracarboxylic acid and/or its derivative is less than 10 mol% in the acid component, the imide component As a result, the heat resistance of the polyamide-imide resin composition decreases.

On the other hand, if the dicarboxylic acid and/or its derivative is less than 10 mol % in the acid component, the amide component will be small and the mechanical properties will be deteriorated.

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.

Examples of such diisocyanates include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisonanate, nonamethylene diisocyanate, decamethylene diisonanate, Trimethylhexamethylene diisocyanate, morpholine diisocyanate, cyclohexane diisocyanate, 3,9-bis(3-propyl isocyanate)-2,4,8,10-tetraoxaspiro(
5,5) Aliphatic and alicyclic diisocyanates such as undecane, 4,4'-diphenylmethane diisocyanate,
4.4'-diphenyl ether diisocyanate), 4.
4'-diphenylpropane diisocyanate, 4.4'
-diphenylsulfone diisocyanate, 3,3'-diphenylsulfone diisocyanate, 4,4'-diphenylsulfite diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3
゜3'-dichloro-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-bisphenyl diisocyanate, 3,3'-dimethoxy-4,4
'- and sphenyl diisocyanate, 4,4'-bisphenyl diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 2.4-tolylene diisocyanate, 2゜6-tolylene diisocyanate, m-xylene diisocyanate, p- There are aromatic diisocyanates such as xylylene diisocyanate, which can be used alone or in a mixture of two or more.

Also usable are diisocyanate derivatives in which the isocyanate groups of diisocyanate are masked with phenols such as phenol, cresol, and xylenol.

Note that, if necessary, part of the diisocyanate and /7 or its derivatives may be replaced with 4.4',4'-)liisocyanate-triphenylmethane, 2.2',5.5'-tetrylananate-4 , 4'-dimethyldiphenylmethane and the like can also be substituted with trivalent or higher polyisocyanates.

Among these isocyanate compounds, 4,4'-diphenylmethane diisocyanate, 2.4-) lylene diisocyanate, 2.6-
) lylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate), 4.4'-
It is particularly preferable to use diphenyl ether diisocyanate or the like alone or in combination of two or more.

The temperature and time for the reaction of polycarboxylic acids containing citric acid and/or their derivatives with diisocyanates and/or their derivatives vary depending on the starting materials and the type of reaction, such as whether the solution reaction is a solventless reaction or not, but in general, the reaction time is The temperature is suitably 60 to 350°C, and the reaction time is suitably several hours to several tens of hours.

The reaction temperature and time in a solution reaction are affected by many factors such as the solvent used, the solid content when charging the starting materials, and the presence or absence of a catalyst, but the decarboxylation reaction between a carboxylic acid or its derivative and a diisocyanate is approximately 70°C. Starting from
Further, in consideration of the boiling point range of the solvent generally used in this reaction, the preferable reaction temperature range is 70 to 250°C.

If the reaction time is extremely long, the incyanate group and the solvent,
Since side reactions such as reactions between isocyanate groups occur, this is not preferable, and a period of several hours to 30 hours is preferable.

The reaction in the present invention can also be carried out without a solvent, and in that case, the reaction can generally be carried out at a lower temperature and in a shorter time than in a solvent reaction.

However, solution reaction is more preferred in view of the ease with which the desired high blood concentration can be obtained and the manner in which the resulting resin composition is used.

As the solvent used in the solution reaction, many organic solvents can be used since the resin composition of the present invention has excellent solubility.

Examples of suitable solvents include phenol, O-cresol, m-cresol, p-cresol, various xylenols, various chlorophenols, nitrobenzene, N
-Methyl-2-pyrrolidone, N,N'-dimethylformamide, N,N'-dimethylacetamide, hexamethylphosphoramide, dimethylsulfoxide, etc., and solvents that can be used in combination with these include benzene, toluene, +V-lene, High boiling point aromatic hydrocarbons (e.g. Maruzen Sekiyu Swasol $1000, Cresol #150
0, Nippon Oil Co., Ltd., Nisseki Heizol 100.1 stone Hysol 150, etc.), monomethyl ether acetate, diethylene glycol monopterether, ethylene glycol 7ofynyl ether, etc.

Particularly preferable solvent compositions are based on the stability of the resulting resin solution,
For economical reasons, it is a mixture of a phenolic solvent such as phenol, cresol, xylenol, etc. and a high boiling point aromatic Group 1 hydrocarbon solvent.

There is no particular restriction on the solid content concentration during the reaction, and the synthesis can be performed without a solvent.

However, in order to obtain a high polymer, a concentration of at least 35% is preferred to prevent side reactions.

The reaction of the invention can be promoted by catalysts commonly used for reactions of this type.

Examples of suitable catalysts include lead monoxide, boric acid, metal salts of naphthenic acids such as lead naphthenate, zinc naphthenate, phosphoric acid,
Examples include polyphosphoric acid, organic titanium compounds such as tetrabutyl titanate and triethanolamine titanate, triethylamine, and 1,8-diaza-bicyclo(5.4.0) undecene-7 (including this acid adduct).

A suitable amount to be used is 0.01 to 5% based on the solid content at the time of preparation, and there are no particular restrictions on the method of addition.

The molar ratio of the polycarboxylic acid containing citric acid and/or its derivative to the diisocyanate and/or its derivative is preferably approximately 1.

However, an excess of about 10 mol % or less of either one is within an acceptable range.

The polycarboxylic acid containing citric acid and/or its derivative and the diisocyanate and/or its derivative may be charged simultaneously from the start of the reaction, or one may be dissolved and the other may be charged at once or in several batches. Yes, there are no particular restrictions on the preparation method.

The reaction can be controlled by observing the bubbling of generated carbon dioxide, the degree of wetting of reaction water, and the viscosity of the solution.

The masked polyisocyanate that can be added to the reaction product of the polycarboxylic acid containing citric acid and/or its derivative obtained in the above reaction and the diisocyanate and/or its derivative is the diisocyanate and/or its derivative. their dimers, dimers, or 4,4',
4'-triisocyanate-triphenylmethane, 2
, 2', 5, 5'-tetraisocyanate-4,4
It is obtained by the reaction of polyisocyanate such as '-dimethyldiphenylmethane with phenols, aliphatic or alicyclic monoalcohols.

It is also possible to use a compound obtained by reacting a polyol in an excess amount of polyisocyanate in an equivalent ratio and masking the compound with a phenol (for example, AP Stable (trade name, manufactured by Bayer), etc.).

Among masked polyisocyanates, aromatic diisocyanates, their dimers, and dimer aromatic polyisocyanates are preferred from the viewpoint of heat resistance and ease of dissociation of the mask body during coating film formation. , cresol,
Compounds masked with phenolic compounds such as xylenol are particularly preferred.

These masked aromatic polyisocyanates can be easily obtained by reacting a polyisocyanate with a phenol compound in an amount of 1 mole or more per inocyanate group at 160 to 250°C for several minutes to several hours.

There is no particular restriction on the temperature when adding the masked aromatic polyisocyanate to the polyamide-imide resin solution, but
If the resin solution is added at around 00°C and stirred for a long time, the resin solution may become opaque and precipitate may occur, so the addition temperature is preferably 140°C or lower.

The amount added is 10% of the resin content of the polyamideimide resin solution.
It is preferably 5 to 150 parts by weight in terms of polyisocyanate before being masked relative to 0 parts by weight.

If it is less than 5 parts by weight, the flexibility and adhesion of the insulated wire will not be improved, and the thermal softening temperature will not increase.

On the other hand, if it exceeds 150 parts by weight, the appearance deteriorates and at the same time wear resistance decreases.

In the case of aromatic diisocyanates masked with phenols, the amount added is particularly preferably from 8 to 120 parts by weight.

The resin composition of the present invention can also be made into a modified polyamide-imide resin by adding polyester resin, phenol resin, evoquin resin, etc.

The present invention is an aromatic polyamideimide resin that exhibits extremely excellent solubility even in phenolic solvents by using polycarboxylic acids containing citric acid and/or derivatives thereof, and is soluble only in conventional organic polar solvents. Heat resistance C; superior to insulation paints, impregnated resins, laminates,
Not only can it be used for electrical insulation materials such as films and adhesives, but also
It can also be applied to the fields of heat-resistant paints, fibers, and molded resins, making it extremely useful in practice.

The present invention will be explained below with reference to Examples.

(I) (Synthesis of masked 4,4'-diphenylmethane diisocyanate) 4. 50 g of 4'-diphenylmethane diisocyanate 250 g of m-cresol The above ingredients were added to an IJ equipped with a thermometer, stirrer, cooling tube, and nitrogen introduction tube.
The mixture was placed in a 4-tube flask and heated and stirred at 200° C. for 30 minutes in a nitrogen stream.

When a part of the contents was taken out and examined for infrared absorption spectrum, the absorption of free isocyanate at 2260 m-' disappeared, and the formation of masked 4,4'-diphenylmethane diisocyanate was observed.

(6) (Synthesis of masked tolylene diisocyanate) Tolylene diisocyanate 1749m-cresol 261g The above ingredients were measured using a thermometer.
A 114-meter flask equipped with a stirrer, a cooling tube, and a nitrogen inlet tube (two people heated and stirred at 200° C. for 1 hour in a nitrogen stream).

When a part of the contents was taken out and the infrared absorption spectrum was examined, the absorption of free isocyanate at 22,600 nm disappeared, and the formation of masked tolylene diisocyanate was observed.

Example 1 In a 314 Tulo flask equipped with a temperature needle, a stirrer, and a cooling tube, 19.29 fl (0.1 mol) of citric acid anhydride, 172.8 fl (0.9 mol) of trimellitic anhydride, and 4.4
'-diphenylmethane diisocyanate 250.3,
P (1.0 mol) and 400 g 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 at around 70°C, and slight wetting was observed at around 160°C.

The reaction was continued for 22 hours while wetting out a small amount of cresol at the reflux temperature of cresol (200-210°C).

The resin solution was clear during the reaction.

Further, the amount of cresol dripped out was 100 g.

Next, m-cresol 8509 was added and thoroughly stirred to obtain a solution with a nonvolatile content (200°C x 1.5 H) of 23.3% and a viscosity (2
A reddish-brown transparent resin solution with 55 voids (5°C) was obtained.

Add the mask body Z obtained in (1) to this resin solution ioo g.
3.3 g (50 electric parts in terms of diisocyanate) and 25 g of m-cresol were added and stirred at 70°C for 30 minutes.

The resulting resin solution was placed on a 0.11111-thick copper plate.
The coating film obtained by baking at 00°C for 20 minutes and 250°C for 30 minutes has sufficient flexibility, and its infrared absorption spectrum contains 1780 (m"" E imide group, 1650 (
m'1: 22601-1 with absorption of 7 mido groups
A slight absorption of isocyanate groups was observed in each case.

In addition, the obtained resin solution was added to 1. When coated and baked on OM$ annealed copper wire, it showed sufficient flexibility even at high wire speeds.

Its characteristics are shown in Table 1.

Example 2 Anhydrous citric acid 38.49 (0.2 mol) was placed in a 314 Tulo flask equipped with a thermometer, stirrer, cooling tube, and nitrogen inlet tube.
, trimellitic anhydride 153.7, F (0.8 mol), 4,4'-diphenylmethane diisocyanate 2
50.3 fj (1,0 mol), m-cresol 40
0 g 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 wetting water was observed from around 160°C.

The reaction was continued at 200°C for 15 hours.

The resin solution was clear during the reaction.

Next, 350 g of cresol and 330 g of solvent naphtha (Maruzen Sekiyu Tokuswasol $1000) were added and thoroughly stirred to remove the non-volatile content (200°C x 1.5 H').
A reddish-brown transparent resin solution with a viscosity (25° C.) of 8.0% and 81 voids was obtained.

Mask body 4 obtained in (I) was added to 100 g of this resin solution.
4 g (78.6 parts in terms of diisonanate) and 45 g of m-cresol were added and stirred at 70°C for 30 minutes.

The resulting combined solution was placed on a copper plate with a thickness of 200 mm.
The coating film obtained by baking for 20 minutes at ℃ and 30 minutes at 250℃ has sufficient flexibility, and its infrared absorption spectrum shows an imide group at 178Q Cm-' and an imide group at 1650 tx-
In addition to the absorption of amide groups at ', a slight absorption of isocyanate groups was observed at 2260 cm.

When the obtained resin solution was coated and baked on a copper wire of 1.01 EII da, it showed sufficient flexibility even at high wire speeds.

Its characteristics were as shown in Table 1.

Examples 3 to 6 Using the resin solution obtained in Example 1 before adding the mask body, resin solutions were obtained by changing the blending amount and type of the polyisocyanate mask body.

The results are shown in Table 2.

Further, the characteristics of the insulated wire obtained in the same manner as in Example 1 were as shown in Table 1.

Example 7 Anhydrous citric acid was added at 48 ml to a 314 Turow flask equipped with a temperature needle, stirrer, cooling tube, and nitrogen inlet tube. Ofl (0.25 mol), trimellitic anhydride 48.0 g (0.25 mol), 3.3', 4.4'-benzophenonetetracarboxylic anhydride 161.5 II (0.5 mol) , 4.4
'-Diphenylmethane diisocyanate 250.3 #
(1.0 mol) and m-cresol (400 f/) 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℃, and further
Distilled water was observed to occur as the temperature reached 70°C.

After this, the reflux temperature of m-cresol (200-210℃)
The reaction was continued for 13 hours.

The hot liquid during the reaction was clear and the viscosity increased over time.

After the reaction, m-cresol 700g, solvent naph 7
(Maruzen Sekiyu, Cresol #1000) 130
9 was added, stirred thoroughly, and the non-volatile matter (200℃
) 24.5%, viscosity (25° C.) A reddish-brown transparent resin solution of SO voids was obtained.

To this resin solution 1009 (mask body 4 obtained by IO).
3 g was added and thoroughly stirred at room temperature to obtain a homogeneous solution.

The obtained resin solution was placed on a copper plate with a thickness of 200 mm.
The coating film obtained by baking for 20 minutes at ℃ and 30 minutes at 250℃ has sufficient flexibility, and its infrared absorption spectrum contains an imide group at 1780 clL-' and an imide group at 1650 (f
Absorption of fi-'E amide group was observed in each case.

Furthermore, when the obtained resin solution was coated and baked on a 1.0io1 dollar annealed copper wire, it showed sufficient flexibility even at high wire speeds.

Its characteristics were as shown in Table 1.

Example 8 38.4 g (0.2 mol) of anhydrous citric acid was placed in a 314 Tulo flask equipped with a thermometer, stirrer, cooling tube, and nitrogen inlet tube.
, trimellitic anhydride 115-3 g (0.6 mol)
, 3.3',4.4'-benzophenonetetracarboxylic anhydride 64.4.9 (0.2 mol), 4,4'-
Diphenylmethane diisocyanate 250.3.9 (
1.0 mol), m-cresol 400, and p 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℃, and further
Formation of distilled water was observed at 70°C.

After reacting at 200°C for 16 hours, m-cresol 50
0 g, solvent naphtha (Maruzen Sekiyu Swazol #1
000) 360! Add i and stir thoroughly to obtain a solution with a non-volatile content (200℃ x 1.s H) of 23.0% and a viscosity (2.
A reddish-brown transparent resin solution with 63 voids (5°C) was obtained.

The mask body 23 obtained in (1) is added to this resin solution 1009.
g was added thereto and thoroughly stirred at 100°C for 10 minutes to obtain a homogeneous solution.

The resulting resin solution was baked on a 0.10-thick copper plate at 200°C for 20 minutes and at 250°C for 30 minutes.The resulting coating film had sufficient flexibility, and its infrared absorption spectrum showed
Imide group at 80cx-', 1650 (m″″1
Absorption of amide groups was observed in each case.

In addition, the obtained resin solution was added to 1. The properties of the insulated wire obtained by coating and baking on annealed copper wire of .

Example 9 11.5 g (0.06 mol) of citric acid anhydride and 19.2.9 g (0.1 mol) of trimellitic anhydride were placed in a 374 tube flask equipped with a temperature needle, stirrer, cooling tube, and nitrogen inlet tube. ), 3,3',4,4'-benzophenonetetracarboxylic anhydride 45.19 (0,14 mol), butanetetracarboxylic acid 163.9 / (0,7 mol), 4.4
'-Diphenylmethane diisocyanate 150.29
(0.6 mol), tolylene diisonanate 69.7
(0-4 mol) and 400 g of m-cresol were charged and the temperature was raised to 185°C over about 1 hour in a nitrogen stream.

Significant foaming was observed from around 70℃, and further from 160℃
A large amount of distilled water was observed to be produced up to 185°C.

The reaction was continued for 14 hours at 185° C. while removing distilled water.

After about 10 hours of reaction, almost no distilled water was produced.

m-Cresol SOO, @, Solvent Naphtha (Maruzen Sekiyu Co., Ltd., Cresol $1000) 180.9 was added and thoroughly stirred to remove the non-volatile content (200℃ x 1.5H) 2
A reddish-brown transparent resin solution with a 0.0% viscosity (25° C.) and 47 voids was obtained.

Add the mask body 2 obtained in (1) to this resin solution ioo g.
8 g was added and thoroughly stirred at 70°C for 30 minutes to obtain a homogeneous solution.

The resulting resin solution was baked on a 0.1-inch thick copper plate at 200°C for 20 minutes and at 250°C for 30 minutes.The resulting coating film had sufficient flexibility, and its infrared absorption spectrum 17
Absorption of an imide group was observed at 80m-1, and a slight absorption of an amide group was observed near 1650m-1.

In addition, the obtained resin solution was added to 1. The properties of the insulated wire obtained by coating and baking Qiua 51 copper wire were as shown in Table 1.

Example 10 In a 3/4 flask equipped with a thermometer, stirrer, and condenser, citric acid anhydride 38.49 (0.2 mol), trimellitic anhydride, 134.5 F < 0.7 mol), terephthal. acid 16.611 (0.1 mol), m-Frezy 4
Prepare 400g and heat to 200℃ for about 1 hour in a nitrogen stream.
The temperature rose to .

Significant foaming was observed from around 70°C, and oily water was observed from around 160°C.

The reaction was continued for 20 hours at the reflux temperature of cresol (200-210°C).

During the reaction, the hot liquid was clear and the viscosity gradually increased.

Add 650 g of m-cresol and stir thoroughly to remove non-volatile content (
A reddish-brown transparent resin solution with a viscosity (25°C) of 65 voids and a viscosity (25%) of 25% (200°C x 1.5H) was obtained.

25 g of Millionate MS-50 (manufactured by Nippon Polyurethane) was added to 100 g of this resin solution and thoroughly stirred at 80° C. for 10 minutes.

The resulting resin solution was heated at 200°C on a 0.1 nm thick copper plate.
The coating film obtained by baking at 250℃ for 30 minutes and 250℃ for 30 minutes has sufficient flexibility, and its infrared absorption spectrum is 1.
Imido group at 780 cIL-', 1650 (X-
' Absorption of amide groups was observed in each case.

Further, the properties of the insulated wire obtained by coating and baking the obtained resin solution on a 1.0IIIO annealed copper wire were as shown in Table 1.

Example 11 Anhydrous citric acid 38.49 (0.2 mol) was added to a 314 Tulo flask equipped with a thermometer, stirrer, cooling tube, and nitrogen introduction tube.
trimellitic anhydride 153.79 (0.8 mol),
4,4'-diphenylmethane diisocyanate) 200
．． 2, p (0.8 mol), 4,4'-diphenyl ether diisonanate 25-21 (0.1 mol),
xylylene diiso νane) 18.8 g (0.1 mol), boric acid 4.9. 400 g of m-cresol 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 bubbling water was observed from 160 to 170°C.

The reaction was continued at 200°C for 10 hours.

Next, Cresol 680 I! , solvent naphtha (Maruzen Sekiyu Swasol #1000) 3009 was added and thoroughly stirred to remove the nonvolatile content (200°C x 1.5 H).
A reddish brown transparent resin solution of 2G, 1%, viscosity (25° C.) 45 voids was obtained.

To 100.9 g of this resin solution were added 8 g of the mask obtained in (I[) and 8 y of m-cresol, and the mixture was thoroughly stirred at room temperature to obtain a uniform solution.

The resulting resin solution was baked on a 1fi thick copper plate at 200°C for 20 minutes and at 250°C for 30 minutes.The resulting coating film had sufficient flexibility, and its infrared absorption spectrum was 17.
80 (X7” E imido group, 1650 cR-'
Absorption of niamide groups was observed in each case.

The properties of the insulated wire obtained by coating and baking the obtained resin solution on a 1.0 m x $ annealed copper wire were as shown in Table 1.

Comparative Example 1 Using the resin solution obtained in Example 1 before adding the mask body, an insulated wire was obtained under the same conditions as in Example 1.

Its characteristics were as shown in Table 1.

Comparative Example 2 An insulated wire was obtained under the same conditions as in Example 2 using the resin solution obtained in Example 2 before adding the mask body.

The viscosity was as shown in Table 1.

Table 1 Note: The insulated wire has a coating thickness of 38μ at a furnace length of 7m and a furnace temperature of 400℃.
Manufactured to be.

The insulated wire test was carried out in accordance with J I8 C3003.

Table 2

Claims (1)

[Claims] 1. A polyamide-imide characterized by adding a polyisonanate compound which is a reaction product of a polycarboxylic acid containing citric acid and/or a derivative thereof and a diisocyanate and/or a derivative thereof, and which is venimasked. Resin composition. 2. The polyamide-imide resin according to claim 1, wherein the polycarboxylic acid containing citric acid and/or its derivative contains at least 5 mol% of citric acid, and the remainder is aromatic tricarboxylic acid and/or its derivative. Composition. 6. The polycarboxylic acid and/or its derivative containing citric acid contains 10 mol% to 90 mol% of the tricarboxylic acid and/or its derivative containing citric acid, and 90 mol% to 90 mol%.
The polyamide-imide resin composition according to claim 1 or 2, which contains 1O mol % of tetracarboxylic acid and/or its derivative. 4. The polycarboxylic acid and/or its derivative containing citric acid contains 10 mol% to 90 mol% of tricarboxylic acid and/or its derivative containing citric acid, and 90 mol% to 1
The polyamide-imide resin composition according to claim 1 or 2, which contains 0 mol% of dicarboxylic acid and/or its derivative. 5. The polyamide-imide resin composition according to any one of claims 1 to 4, wherein the aromatic tricarboxylic acid and/or its derivative is trimesitic anhydride. 6. Claim 1, wherein the diisocyanate and/or its derivative is an aromatic diisocyanate and/or an aromatic diisocyanate masked with a phenol.
The polyamide-imide resin composition according to any one of Items 1 to 4. 7. aromatic diisocyanate and/or its derivative; 4. ．． 4'-diphenylmethane diisocyanate, 4
, 4'-diphenyl ether diisocyanate, tolylene diisocyanate, or xylylene diisocyanate, and one or two diisocyanate derivatives in which these diisocyanates are masked with phenols.
The polyamide-imide resin composition according to any one of claims 1 to 6, comprising at least one species. 8. The masked polyisocyanate compound added to the reaction product of a polycarboxylic acid containing citric acid and/or its derivative and a diisocyanate and/or its derivative is an aromatic polyisocyanate compound masked with a phenol, and The blending amount is 1 part for the reaction generated resin.
5 to 00 parts by weight in terms of polyisocyanate
150 parts by weight of the polyamide-imide resin composition according to any one of claims 1 to 7. 9. A polycarboxylic acid containing citric acid and/or its derivative and an aromatic diincyanate and/or its derivative are heated and reacted in a phenolic solvent, and then a phenol is added to 100 parts by weight of the resin content of the reaction product. A method for producing a polyamide-imide resin, characterized in that 5 to 4150 parts by weight, calculated as polyisocyanate, of an aromatic polyisocyanate masked with is added at a temperature of 140° C. or lower. 10. The method for producing a polyamide-imide resin according to claim 9, wherein the polycarboxylic acid containing citric acid and/or its derivative is trimellitic acid anhydride containing at least 5 mol % of citric acid.