JPS5950187B2 - water soluble paint - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to water-soluble polyesterimide resins and polyesteramideimide resins.

These resins are useful as heat-resistant insulating paints. Conventionally, polyesterimide resins have been used as paints, and many manufacturing methods are known, but there has been a need for something even better in terms of heat resistance and impact resistance. The present inventors focused their studies on solving these points, and found that when producing polyesterimide resin or polyesteramideimide resin, the molar ratio of symmetrical to asymmetrical polyhydric alcohol used as a raw material was 1. :1 to 6:1 dihydric alcohol and 0.2 to this dihydric alcohol
A water-soluble paint obtained by producing polyesterimide or polyesteramideimide resin using a polyhydric alcohol consisting of 5 to equimolar amount of trihydric alcohol, neutralizing this with a base, and adding a crosslinking agent to this is heat-resistant. It was discovered that it has excellent properties as an insulating paint in terms of durability and impact resistance.

Next, the paint in the present invention will be explained in detail.

According to the present invention, when polyesterimide or polyesteramideimide resin is reacted with a polyhydric alcohol and a polybasic acid, (1) using a polyhydric alcohol containing imide alcohol or amide-imide alcohol, (2) imide acid Or using amidoimidic acid,
Alternatively, (3) a corresponding resin can be obtained by adding imidic acid alcohol or amidimidic acid alcohol.

As a polyhydric alcohol, 0.0% per mole of dihydric alcohol.
25 to equimolar amounts of trihydric alcohol are used.

A symmetric dihydric alcohol is used 1 to 6 times more than an asymmetric dihydric alcohol. Ethylene glycol, diethylene glycol, neopentyl glycol, hydroxypivalyl hydroxypivalate, 1,4-butanediol, etc. are used as symmetrical dihydric alcohols. Examples of asymmetrical dihydric alcohols are propylene glycol, 1,4-butanediol, etc.
, 3-butanediol. If the ratio of symmetrical dihydric alcohol to asymmetrical dihydric alcohol is less than 1, the appearance of the film will be poor, and if it is greater than 6, storage stability and thermal shock resistance will be poor.

As the Ξ alcohol, glycerin, trimethylolprotane, trimethylolethane, hexanetriol, tris(2-hydroxyethyl)-isocyanuric acid, etc. are used.

Suitable polybasic acids include terephthalic acid, trimellitic acid, pyromellitic acid, or their acid halides, such as terephthalic acid cyclolade and trimellitic acid chloride, lower alkyl esters, such as dimethyl terephthalate, and acid anhydrides, such as trimellitic anhydride. used.

By using these polybasic acids in combination with adipic acid, glutaric acid, isophthalic acid, or their acid halides, acid anhydrides, and lower alkyl esters, the flexibility of the product is improved.

Imidic acid used in the present invention means a dibasic acid having at least one imide ring in one molecule, for example, 2 moles or more of trimellitic anhydride and 1 mole of a diamine compound or diisocyanate compound. By reacting with 1 mole of pyromellitic anhydride, a carboxylic acid compound 2 having an amino group or an isocyanate group in one molecule can be obtained.
It can be easily synthesized by reacting with mol or more.

Imidic acid alcohol has one or more imide rings in one molecule,
It is a compound that has a hydroxyl group and a carboxyl group, and is synthesized by the reaction of trimellitic acid and an amino alcohol. Imide alcohol is a polyhydric alcohol having one or more imide rings in one molecule, and is synthesized by the reaction of pyromellitic anhydride and amino alcohol.

Amidimide acid is a dibasic acid having one or more amide groups and imide rings in one molecule, and trimellitic anhydride or its halide and a diamine compound or isocyanate compound are mixed in an acid content of 1 to 2 times the molar excess. React or
Furthermore, it can be obtained by reacting the system with a combination of a dibasic acid or its dihalide or pyromellitic anhydride.

Amidimide alcohol is a polyhydric alcohol having one or more amide groups and imide rings in its molecule, and is obtained by reacting trimellitic anhydride halide with an amino alcohol.

Diamine compounds include phenylene diamine, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfone, hexamethylene diamine, ethylene diamine, etc. Diisocyanate compounds include toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate. etc. can be mentioned.

Carboxylic acid compounds having an amino group or an isocyanate group in one molecule include aminobenzoic acid, ω-aminohexanoic acid, glycine, etc., and are compounds in which these amino groups have become an isocyanate group.

Ethanolamine, propanolamine, etc. are used as the amino alcohol. The reaction between the polyhydric alcohol and the polybasic acid is carried out under generally known conditions for esterification and transesterification reactions.

That is, in the case of esterification reaction, 100%
The reaction is carried out at ~300°C while distilling off the produced water. It is possible to use an azeotropic dehydrating agent such as benzene or xylene in order to prevent the contents from sublimating and to speed up the distillation of the produced water. The transesterification reaction is carried out at 100 to 300°C in a suitable solvent in the presence of a catalyst usually used for transesterification, such as lead acetate or risarge.

Imidic acid, imidic acid alcohol, imide alcohol, amide imide acid, amide imide acid alcohol, and amide imide alcohol can be added themselves to the above reaction, but the desired product can also be obtained by adding raw materials for synthesizing these and reacting them. .

The amounts of polyhydric alcohol and polybasic acid used are usually equivalent to alcohol excess, but preferably the total number of hydroxyl groups is 1 to 1.3 times the total number of carboxylic acid groups. desirable.

The reaction is carried out so that the acid value of the polyester resin obtained is 30 or more. If the oxidation value is less than 30, the water solubility of the resin will be poor. The obtained polyester resin is made water-soluble by neutralizing it with a base such as ammonia or an amine.

In this case, polyester resin can be used with cellosolve or
Neutralize by dissolving in a water-soluble solvent such as cellosolve acetate. The polyester insulation coating of the present invention can be obtained by adding a crosslinking agent to the water-soluble polyester resin obtained by combing.

As a crosslinking agent, a hydrophilic organic titanium compound such as a titanate ester such as titanium tetrabutoxide or titanium tetraisopropoxide, or a chelate compound such as titanium lactic acid, acetylacetone, or triethanolamine is used.

These organic titanium compounds are used in an amount of 0.2 to 3.0% by weight, preferably 1.0 to 2.0% by weight in terms of titanium metal, based on the polyester resin.

When the amount used is less than 0.2% by weight, sufficient performance as an insulating coating cannot be exhibited, and when it exceeds 3.0% by weight, flexibility deteriorates. Examples illustrating aspects of the present invention are shown below.

Example 1 1.1 with stirrer, thermometer and cooler with side tube installed
Add 134% dimethyl terephthalate (DMT) to the flask.
3g (0.69 mol), neobentyl glycol 78.
59 (0.75 mol), propylene glycol 16.7
9 (0.22 mol), trimethylolpropane 42.2
f! (0.31 mol), xylene 10f1 and lead acetate (
(0.1% by weight based on DMT) was added, and the temperature was raised and melted while stirring while blowing nitrogen gas.

Heating was carried out at 170-180°C for 3 hours and then at 00°C for 1 hour, during which time methanol was distilled off.

Next, the temperature was raised to 150°C, and 29.09 (0.15 mol) of 4,4'-diaminodiphenylmethane and 56.3 f of trimellitic anhydride! (0.29 mol) was added, the temperature was immediately raised to 210-215°C, and heating was continued for 4 hours while removing the produced water. During this time, the reaction solution, which had become yellow and muddy due to the formation of the imide compound, became transparent and brown. Then the temperature was lowered to 180°C and trimellitic anhydride 48.39%
(0.25 mol) was added, and a super viscous resin with an acid value of 63.6 was obtained by reaction at 190 to 200°C for 1 hour. This was dissolved in 150 g of butyl carbitol, neutralized by adding 37.79 g of dimethylaminoethanol, and then made water-soluble with 300 g of water.
After adding 51.59% of titanium acetylacetone complex, water was further added to give a non-volatile content of 31.7% and a viscosity of 20 voids (
A varnish of 30 C) was obtained. Example 2 Dimethyl terephthalate 129.19 (0.67
mol), neopentyl glycol 75.59 (0.73
mol), propylene glycol 16.1 g (0.21 mol), tris-2-hydroxyethyl-isocyanuric acid 19.69 (0.08 mol), glycerin 20.99 (
0.23 mol), xylene 109, and lead acetate (0.1% by weight based on DMT) were added, and the temperature was raised and melted while stirring while blowing nitrogen gas.

Heating was carried out at 170-180°C for 3 hours and then at 200°C for 1 hour, during which time methanol was distilled off.

Next, the temperature was lowered to 150 °C, 29.09 (0.15 mol) of 4,4'-diaminodiphenylmethane and 56.3 f1 (0.29 mol) of trimellitic anhydride were added, and the temperature was immediately lowered to 210-215 °C. ℃ and continued heating for 4 hours while removing produced water.

During this time, the reaction, which had turned yellow due to the formation of an imide compound, turned into a transparent brown color. Next, the temperature was raised to 180°C, 46.5f1 (0.24 mol) of trimellitic anhydride was added, and the reaction was carried out at 190-200°C for 1 hour to obtain an ultra-viscous resin with an oxidation rate of 63.6. This was dissolved in butyl carbitol 2009, and 38.4 g of dimethylaminoethanol was added to neutralize it, followed by solubilization with 300 g of water. After adding 51.59 of the titanium acetylacetone complex, water was further added to reduce the non-volatile content to 3.
A varnish with a viscosity of 5.4 (I) and a viscosity of 25 poise (30° C.) was obtained. Example 3 In an apparatus similar to Example 1, 120% of dimethyl terephthalate was added.
6g (0.62 mol), neopentyl glycol 70.
59 (0.68 mol), propylene glycol 15.0
9 (0.20 mol), tris-2-hydroxyethyl-
73.8 f1 (0.28 mol) of isocyanuric acid, 10 g of xylene, and lead acetate (0.1% by weight based on DMT) were added, and the temperature was raised and melted while stirring while blowing nitrogen gas.

Heating was carried out at 170-180°C for 3 hours and then at 200°C for 1 hour, during which time the methanol was distilled off.

Next, the temperature was lowered to 150°C, 29.09 (0.15 mol) of 4,4'-diaminodiphenylmethane was added, the temperature was immediately raised to 210-215°C, and heating was continued for 4 hours while removing the water produced. continued.

During this time, the reaction solution, which had become yellow and muddy due to the formation of an imide compound, turned transparent and brown. Next, the temperature was lowered to 180°C and 43.49 (0.23 mol) of trimellitic anhydride was added.
A super-viscous resin with an acid value of 63.0 was obtained by reaction at 190-200°C for 1 hour. This was dissolved in 200 g of butyl carbitol, 37.99 g of dimethylaminoethanol was added, and after neutralization, the solution was made water-soluble with 300 g of water. After adding 51.59 g of titanium acetylacetone complex, water was further added to obtain a varnish with a non-volatile content of 34.8% and a viscosity of 33 voices (30° C.). Example 4 Titanium tetrabutoxide was added to the butyl carbitol solution of polyesterimide obtained in Example 2 at 100°C.
9 was added and kept for 1 hour.

Thereafter, 38.4 fl of dimethylaminoethanol was added and water was added to obtain a varnish with a nonvolatile content of 32.7% and a viscosity of 39.1 poise (30° C.). Example 5 In an apparatus similar to Example 1, 165% of dimethyl terephthalate was added.
3f1 (0.85 mol), neopentyl glycol 9
6.79 (0.93 mol), propylene glycol 2
0.69 (0.27 mol), tris-2-hydroxyethyl isocyanuric acid 101.19 (0.39 mol)
, xylene 109, and lead acetate were charged, and the same transesterification reaction as in Example 1 was carried out in a nitrogen gas-injected chamber.

Next, the temperature was lowered to 110°C, and ethylenediamine 10.8
f1 (0.18 mol), trimethic anhydride 19.09
(0.36 mol) was added. Immediately raising the temperature, imidic acid was produced from about 160°C. 210~2 as is
After raising the temperature to 15°C and keeping it for 3 hours, it was heated to 180°C and 59.5y (0.31 mol) of trimellitic anhydride was added.
Heating was continued at 190-200°C until the acid value reached 63.2. The produced resin was dissolved in 180 g of butyl carbitol, neutralized by adding 49.69 g of dimethylaminoethanol, and then made water-solubilized with 200 fl of water, and 68.29 g of titanium acetylacetone complex was added. The resulting varnish had a nonvolatile content of 49.6% and a viscosity of 22 poise (30°C). Example 6 In an apparatus similar to Example 1, dimethyl terephthalate 144
．． 29 (0.74 mol), neopentyl glycol 8
4.39 (0.81 mol), propylene glycol 18
．． 09 (0.09 mol), tris-2-hydroxyethyl isocyanuric acid 88.2 g (0.34 mol), xylene 10f1, and lead acetate were added, and the same transesterification reaction as in Example 1 was carried out.

Next, the temperature was lowered to 150°C, and p-phenylenediamine 16
．． 99 (0.16 mol), trimellitic anhydride 60.
29 (0.31 mol) was added, the temperature was immediately raised to 210-215°C, and heating was continued for 10 hours while removing the produced water. During this time, the reaction solution, which had become brown and muddy due to the formation of an imide compound, became transparent. Next, the temperature was lowered to 180°C, 51.99 (0.27 mol) of trimellitic anhydride was added, and a super-viscous resin with an acid value of 61.8 was obtained by reaction at 190-200°C for 30 minutes. Add this to Butyl Carbitol 200f1
After neutralizing by adding 43.19 g of dimethylaminoethanol, 300 g of water was added. After adding 60.69 g of titanium acetylacetone complex, water was further added to obtain a varnish with a nonvolatile content of 37.4% and a viscosity of 36 poise (30° C.). Example 7 A) 75 g (1 mol) of glycine in the same apparatus as in Example 1.
, trimellitic anhydride 192f1 (1 mono-O), cresol 4009, and 50 g of xylene were added and heated while stirring while blowing nitrogen gas.

The dehydration reaction starts at about 155℃, but the temperature continues to rise,
The mixture was stirred at 180°C for 4 hours. When the mixture was allowed to cool to room temperature, imidic acid was precipitated. The precipitate was washed with acetone and then dried to obtain 231.69 white powder (yield 93%). B
) Dimethyl terephthalate 176 was added to the same apparatus as in Example 1.
．． 69 (0.91 mol), neopentyl glycol 10
3.39 (0.99 mol), propylene glycol 2
2.09 (0.29 mol), tris-2-hydroxyethyl isocyanuric acid 108.09 (0.41 mol)
, xylene 109, and lead acetate were charged, and the same transesterification reaction as in Example 1 was carried out in a nitrogen gas-injected chamber.

Next, the temperature was lowered to 180°C, 47.99 (0.19 mol) of imidic acid obtained in Example A was added, and immediately 2
The temperature was raised to 10-215°C. After reacting at this temperature for 3 hours,
Lower the temperature to 180℃ again and trimellitic anhydride 63.59 (
0.33 mol) was added thereto and heated and stirred at 190 to 200° C. for 1.5 hours while removing generated water to obtain a resin with an acid value of 45.5. This was dissolved in butyl carbitol 1709, neutralized with 35.79 g of dimenalaminoethanol, and then dissolved in water 200 g.
It became water-soluble at step 9. Furthermore, titanium acetylacetone chain body 68
．． 29 was added to obtain a varnish with a nonvolatile content of 49.7% and a viscosity of 45 poise (30°C). Example 8 In an apparatus similar to Example 1, 176% of dimethyl terephthalate was added.
3y (0.91 mol), neopentyl glycol 10
3.1g (0.99mol), propylene glycol 2
2.09 (0.29 mol), tris-2-hydroxyethyl isocyanuric acid 107.8f1 (0.41 mol)
, 10 g of xylene, and lead acetate were added, and the same transesterification reaction as in Example 1 was carried out.

The temperature was then lowered to 150°C and monoethanolamine 11
．． 79 (0.19 mol), trimellitic anhydride 36.8
g (0.19 mol) and immediately lowered the temperature to 210-21
The temperature was raised to 5° C., and heating was continued for 4 hours while removing produced water. Next, the temperature was lowered to 180°C, 63.4 g (0.33 mol) of trimellitic anhydride was added, and the temperature was lowered to 190-200°C.
A viscous resin with an oxidation rate of 54.7 was obtained after one hour of reaction.
This was dissolved in butyl carbitol 1509, neutralized with dimethylaminoethanol 43.09, and then solubilized with water 3509. Furthermore, titanium acetylacetone complex 68.2f
1, nonvolatile content 42.9%, viscosity 31 poise 1
(30°C) varnish was obtained. Reference Example 1 Dimethyl terephthalate 131.
1 g (0.68 mol), neopentyl glycol 88.
19 (0.86 mol), propylene glycotool 7.5
9 (0.10 mol), trimethylolpropane 41.2
9 (0.31 mol), xylene 109, and lead acetate were added to carry out the same exchange reaction as in Example 1 to form an ester.

Next, the temperature was lowered to 150°C, 28.29 (0.152 mol) of 4,4'-diaminodiphenylmethane and 54.7 g (0.29 mol) of trimellitic anhydride were added, and the temperature was immediately lowered to 210-215°C. Heating was continued for 4 hours while removing the produced water. Next, the temperature was raised to 180°C, 47.29 (0.25 mol) of trimellitic anhydride was added, and 1
A super-viscous resin with an acid value of 621 was obtained by reaction at 90-2005°C for 1 hour. This was dissolved in butyl carbitol 1509, neutralized by adding 36.89 g of dimethylaminoethanol, and then water-solubilized. Absolutely titanium acetylacetone complex 51.5f! After adding water, add water to reduce the non-volatile content to 33.
．． 2 (fl) and a varnish with a viscosity of 27 poise (30° C.) was obtained. The varnish separated after 3 days. Reference Example 2 Dimethyl terephthalate 132.09 was added to the same apparatus as in Example 1.
(0.69 mol), neopentyl glycol 87.59
(0.84 mol), propylene glycol 19.79 (
0.26 mol), trimethylolpropane 28.29 (
0.21 mol), xylene 109, and lead acetate were added, and the same transesterification reaction as in Example 1 was carried out.

Next, the temperature was lowered to 150°C and 28.49 (0.15 mol) of 4,4'-diaminodiphenylmethane and 55.19 (0.29 mol) of trimellitic anhydride were added, and the temperature was immediately raised to 210-215°C. Heating was continued for 4 hours while removing the produced water. Next, the temperature was lowered to 180°C, 47.59 (0.25 mol) of trimellitic anhydride was added, and 19.
A super viscous resin with an acid value of 54.5 was obtained by reaction at 0 to 200°C for 11 hours. This is butyl carbitol 150f! The mixture was dissolved in water and 32.39 g of dimethylaminoethanol was added to neutralize it, and then it was made water-soluble. Next, titanium acetylacetone complex 51.
After adding 59, further water was added to make the non-volatile content 32.8%.
A varnish with a viscosity of 25 poise (30°C) was obtained. Using the water-soluble paint obtained in the above examples and reference examples, it was applied 7 to 8 times by die method onto a copper wire with a diameter of 0.5 mm at a baking temperature of 520°C and a line speed of 27 to 33 m/min, and baked. Table 1 shows the results of manufacturing an insulated wire and investigating the characteristics of the husband's insulated wire.

In addition, as Reference Example 3, the case where no crosslinking agent is used in Example 2 is also described, and as Reference Example 4, a general-purpose solvent-type polyester imide varnish is also described.

Example 9 Dimethyl terephthalate (DM
T) 128.39 (0.66 mol), neobentyl glycol (Itcho NPG) 75.09 (0.72 mol), propylene glycol (Itcho PG) 16.0y (0.2
1 mol), trimethylopropane (hereinafter referred to as TMP) 40.
39 (0.30 mol), xylene 109 and lead acetate (D
(0.1% by weight based on MT) was put in a nitrogen gas blowing knife, and the temperature was raised while stirring to melt it.

Heating was performed at 170-180°C for 3 hours and at 200°C for 1 hour, during which time methanol was distilled off.

Next, the temperature was lowered to 150°C, and 4,4'-diaminodiphenylmethane (Itcho MDA) 46.7θ (0.24 mol), trimellitic anhydride (Ityo TMA) 56.49 (
When 0.29 mol) was added, the reaction solution became brown and opaque. After heating at 170℃ for 2 hours, increase the temperature to 210~21℃.
When held at 5°C for 4 hours, the produced water was removed during this time,
The reaction solution became clear.

Next, the mixture was heated to 180°C, TMA46.29 (0.24 mol) was added, and the temperature was maintained at 190-200°C until the acid value reached 61. The resulting resin is treated with butyl carbitol 2009.
After neutralizing by adding 44.09 g of diethanolamine, 300 g of water, 51.5 g of titanium acetylacetone complex
By adding y and further diluting with water, the nonvolatile content was reduced to 35.
A varnish with a viscosity of 3% and a viscosity of 30 poise (30° C.) was obtained. Example 10 DMT97.2y (0.50 mol) and NPG68. O9 (0.65 mol), PGl4
．． 59 (0.19 mol), tris-(2-hydroxyethyl)-isocyanuric acid (THEIC) 71
．． 29 (0.27 mol), xylene 109, and lead acetate were added, and the same transesterification reaction as in Example 9 was carried out.

Next, the temperature was raised to 150°C and MDA35.9y (0.
18 mol), isophthalic acid (Icho IPA) 18.1 g (
0.11 mol), TMA48.59 (0.25 mol)
added. After holding the temperature at 185°C for 2 hours while removing the produced water, heating at 210-215°C for 3 hours,
During this time, the reaction solution, which had been brown and opaque, became transparent. 1
Stir to 80°C, TMA47. After adding 19 (0.25 mol), the mixture was heated at 190 to 200°C until the acid value reached 53, and the resulting resin was dissolved in 200 g of butyl carbitol.

Dimethylaminoethanol (IchoDMAE) 31.49
was added to neutralize it, and then Ne00y was added to make it water-soluble. After this, 51.59% of titanium acetylacetone complex was added,
By further diluting with water, the non-volatile content is 31.1% and the viscosity is 3.
A 1 poise (30°C) varnish was obtained. Example 11 DMT96.59 (0.50 mol), NPG 67.59 (0.65 mol), 1,3-
Butanediol 17.0y (0.19 mol), THE
IC7O. 6y (0.27 mol), 10 g of xylene, and lead acetate were added, and the same transesterification reaction as in Example 9 was carried out.

Next, the temperature was increased to 150℃, and the MDA was 35.59 (0.1
8 mol), IPAl8. O9 (0.11 mol), TMA
48.2 fl (0.25 mol) was added. After maintaining the temperature at 185°C for 2 hours while removing the produced water, 210°C
The reaction solution, which had been brown and opaque, became transparent during heating at ~215° C. for 3 hours. Next, heat to 180℃, TM
After adding 46.7 g (0.24 mol) of A, 190~
The temperature was raised to 200°C and a reaction was performed to obtain a resin with an acid value of 48.
Dissolve the generated resin with butyl carbitol 2009,
Furthermore, after neutralizing by adding DMAE29.3y, titanium acetylacetone complex 51.59 was added and diluted with water, resulting in a non-volatile content of 36.4% and a viscosity of 30 poise (30°C).
) varnish was obtained. Example 12 Add 1 to the butyl carbitol solution of polyesteramideimide obtained in Example 10.
At 00°C, 36.29 g of titanium tetrabutoxide was added and kept for 1 hour.

After this, DMAE3l. 4,! 9 was added and water was added to obtain a varnish with a nonvolatile content of 32.0% and a viscosity of 34 poise (30° C.). Reference Example 5 DMTIIO. 2g (0.57
mol), NPG87.3y (0.84 mol), PG8
．． 49 (0.11 mol), THEIC8O. 69(
0.31 mol), xylene 109, and lead acetate were added to carry out transesterification reaction.

Next, the temperature was raised to 150°C, and MDA4O. 6y(0.
21 moles).

IPA2O. 59 (0.12 mol), TMA55. O
9 (0.29 mol) was added. The temperature was maintained at 185°C for 2 hours while removing the produced water, and then 210-215°C.
It was heated for 3 hours.

Subsequently, the temperature was lowered to 180°C and 53.49 (0.28 mol) of TMA was added, and then heated at 190 to 200°C until the acid value reached 57, and the resulting resin was mixed with 200 g of butyl carbitol.
dissolved in. After neutralizing by adding DMAE39.89, water was added to make it water-soluble. Thereafter, 60.6y of titanium acetylacetone complex was added and further diluted with water to obtain a varnish with a non-volatile content of 32.3% and a viscosity of 34 poise (30C). This varnish separated the next day. Reference Example 6 DMTll4O9 (0.59 mono(ha), NPG85.l9 (0.82 mol), PG2
O. 49 (0.27 mol), THEIC63.49 (0
．． 24 mol), xylene 109, and lead acetate were added to carry out a transesterification reaction.

Then lower the temperature to 150°C and MDA42. O9 (0.21
mol), IPA2l. 29 (0.13 mol), TMA5
6.99 (0.30 mol) was added. After keeping the temperature at 185°C for 2 hours while removing the produced water,
Heated at 5°C for 3 hours. Subsequently, the temperature was lowered to 180°C, and TMA
After adding 55.29 (0.29 mol), 190-20
The resin was heated at 0° C. until the acid value reached 52, and the resulting resin was dissolved in butyl carbitol 2009. DMAE36.3
f! was added to neutralize it, and then water was added to make it water-solubilized. After that, 60.6 fl of titanium acetylacetone complex was added and further diluted with water to reduce the non-volatile content to 34.8 (fl).
A varnish with a viscosity of 30 poise (30°C) was obtained. Using the water-soluble paints obtained in Examples 9 to 12 and Reference Examples 5 and 6 above, 7 to 8 Insulated wires were manufactured by coating and baking, and the characteristics of each insulated wire were investigated, and the results are shown in Table 2. Note that, as Reference Example 7, Example 10 in which no crosslinking agent was used, and Reference Example 8, in which a general-purpose solvent-type polyester varnish was used, are also described.

Claims (1)

[Claims] 1 When producing polyesterimide resin or polyesteramideimide resin, the molar ratio of symmetry and asymmetry as a polyhydric alcohol is 0.25 to 0.25 to this dihydric alcohol and a dihydric alcohol consisting of 1:1 to 6:1.
A water-soluble paint made by neutralizing the resulting polyesterimide or polyesteramide-imide resin with a base using a polyhydric alcohol consisting of equimolar amounts of trihydric alcohol, and adding a crosslinking agent thereto.