JPS581153B2 - succulents - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-soluble paint composition having excellent heat resistance and flexibility, and particularly to a paint composition suitable for electrical insulation paint.

BACKGROUND ART In recent years, with the miniaturization and higher performance of electrical equipment, the use of heat-resistant paints made of at least one type of heat-resistant paint such as polyesterimide, polyamideimide, polyimide, etc. has become widespread.

Due to the characteristics of the resin, these paints are made of cresol, N-
It is used as a solution-type paint dissolved in an organic solvent with relatively strong dissolving power and a high boiling point, such as methylpyrrolidone, N,N-dimethylacetamide, or xylene.

Organic solvent-based paints have two problems: environmental pollution and economic loss due to solvent dissipation, and two types of paint types, solvent-free and water-soluble, have generally been proposed as a way to avoid these drawbacks. and general-purpose paints are rapidly being replaced.

However, due to the structure of the heat-resistant insulating paint as described above, it cannot be said that a water-soluble paint or a solvent-free paint with sufficient practicality has yet been obtained.

Therefore, the present inventors focused on a polyesterimide type paint that has well-balanced performance as a heat-resistant insulating paint, and as a result of intensive studies, they aimed to create a water-soluble paint composition with excellent practicality. , the present invention has been achieved.

That is, the present invention provides (a) a bistrimelitate diamide represented by the formula (I) (wherein R represents a divalent organic group having 2 to 15 carbon atoms mainly consisting of an aliphatic hydrocarbon residue); At least one of each of the polycarboxylic acid component (b) consisting mainly of anhydride, the amine component having at least two or more 7 primary amine groups, and (c) the polyol compound at a temperature at which imidization does not substantially occur. After the reaction, the remaining carboxyl groups are neutralized to form salts with a basic compound to make them water-soluble.

Attempts have been made to convert polyesterimide paints into water-soluble paints.

Generally, in order to make a polymer that has an imide salt, at least after curing, water-soluble, an amine is added to a cyclic carboxylic acid anhydride group to form a salt of a free carboxylic acid in the form of an amic acid group. method can be used.

This is preferable because after coating, the amic acid bonds are easily imidized by heating and curing, thereby eliminating free carboxyl groups, making it possible to achieve thermal stabilization and water insolubilization at the same time.

On the other hand, trimellitic anhydride is generally used as the polycarboxylic acid component of polyesterimide.

However, when trying to obtain a water-soluble polyesterimide precursor from trimellitic anhydride, a polyamine, and a polyol, imide ring closure occurs before the esterification of the 4-position of trimellitic anhydride, resulting in an efficient and good process. It was difficult to obtain a water-soluble resin.

Therefore, by using a bistrimelitate dianhydride such as the above formula (I) in which the carboxyl group at position 4 has been esterified in advance, and further replacing a part of the polyamine with a polyol compound as a crosslinking component, it is possible to obtain better water-soluble properties. The present inventors have discovered that a composition for use in paints can be obtained.

A general method for producing bistrimelitate dianhydride (a) used in the present invention is (i) a transesterification reaction between trimellitic anhydride and a lower fatty acid ester such as bisacetate of diols (the following formula (See ■) (ii) Method by reaction of 4-chloroformylphthalic anhydride with a diol (see formula III below) iii) Trimellitic anhydride and diol are directly heated at high temperature using at least twice the mole of the former. How to esterify.

In this case, since a considerable amount of by-products are produced, it may be necessary to sufficiently purify the product before use.

Other special manufacturing methods are also possible, but when used in the present invention, they can be used regardless of the manufacturing method.

R in the formula (1) is preferably an alkylene group and/or a polyoxyalkylene group having 2 to 15 carbon atoms, and specific examples include ethylene, tetramethylene, hexamethylene, nonamethylene, decamethylene, dodecamethylene, and diethylene ether. , tetraethylenetriether, β-
Examples include various groups such as acetoxy-trimethylene.

Furthermore, R containing a cyclic group such as each residue of m-xylylene glycol or hexahydrometa-xylylene glycol can also be used.

Note that the bistrimelitate dianhydride used in the present invention does not need to be particularly purified, and may be glycol monotrimelitate anhydride or anhydride whose anhydride group is ring-opened by water or alcohol. There is no problem even if some of the ingredients are mixed in.

Furthermore, a part of the above-mentioned bistrimelitate dianhydride can be used by replacing generally 50 mol% or less, more preferably 30 mol% or less, with another tetracarboxylic dianhydride.

Examples of such tetracarboxylic dianhydrides include butanetetracarboxylic dianhydride, cyclopenkunetetracarboxylic dianhydride, penzophenonetetracarboxylic dianhydride, diphenylsulfonetetracarboxylic dianhydride, and pyromellitic dianhydride. Examples include acid dianhydrides.

The amine component (b) used in the present invention may include aromatic, aliphatic, alicyclic, and Although any mixture thereof may be used, aromatic polyamines are preferred from the viewpoint of heat resistance.

Such aromatic amines include 4,4'-diaminodiphenylmethane, tris(4-amine)diphenylmethane, polymethylene polymethylene polyamine (polycondensate of aniline and formaldehyde), 4,4'-1 or 4,3
'~diaminodiphenyl ether, 2,4,4'-1-
riaminodiphenyl ether, 4,4'- or 3,3'
Examples include -diaminodiphenylsulfone, m- or p-phenylenediamine, and 1,5-diaminonaphthalene.

In addition, these polyamines contain inert substituents such as lower alkyl groups, lower alkoxy groups, and halogen groups, such as 2,4-tolylene diamine and 3,3'-dimethyl-4,4'-diaminodiphenylmethane. There is no problem even if you have one.

Furthermore, examples of aliphatic and alicyclic polyamines include hexamethylene diamine, nonamethylene diamine, ethylene diamine, isophorone diamine, 4,4'-diaminodicyclohexylmethane, cyclohexane-1,4-bis(methylamine), etc. , m- or P-xylylene diamine can be mentioned as a mixed type with aromatic.

The polyol component (c) used in the present invention may be any compound having two or more alcoholic hydroxyl groups, regardless of whether it is a low molecular compound, a low polymer, or a high polymer. It is preferable to have solubility, and it is preferable to use a trifunctional or higher functional compound as at least a part of the component (c).

Specific examples of low molecular weight compounds include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, bis-β-hydroxyethyl terephthalate, glycerin, trimethylolpropane, pentaerythritol, tris(β-hydroxyethyl)in cyanurate, etc. I can give you.

Although polymers having two or more hydroxyl groups in either terminal or pendant groups can also be used, water-soluble polyester oligomers having terminal hydroxyl groups are particularly suitable for this purpose.

Examples of such oligomers include ester oligomers obtained by reacting trimellitic anhydride and isophthalic acid as carboxylic acid components and ethylene glycol and glycerin as polyol components in excess molar amount.

At least a part of the polyol component of the present invention can be replaced with amino alcohols.

Examples of such amino alcohols include ethanolamine, diethanolamine, propanolamine, 2,3
-Hydroxypropylamine etc. can be mentioned.

In particular, compounds having two or more alcoholic hydroxyl groups in one molecule can naturally be included in the definition of polyol components.

(a) and (b) for obtaining a coating polymer in the present invention
) and (c) Regarding the blending ratio of components (b) and (c)
The equivalence ratio between the amine group in the component and the acid anhydride group or its open group in the component (a) depends on the type of raw materials used, the required weight,
Generally 0.1 to 0.95, although it varies depending on the nature of coalescence etc.
The range of 0.5 to 0.9 is particularly preferred for practical purposes.

The amount of hydroxyl groups in component (C) is generally determined by experiment for each composition, within a range that sufficiently reacts with the remaining carboxyl groups that have reacted with the amine groups and provides a cured product with good properties upon baking. I can do it.

Generally, an amount in excess of the number of equivalents of the remaining acid anhydride groups is used, particularly in a range of 1.5 to 4 times.

Polyol compounds such as ethylene glycol, glycerin, and diethylene glycol that are liquid at room temperature, miscible with water, and volatile can also be used as reaction solvents, which will be described later, and the unreacted excess amount can be volatilized during baking. Therefore, it is also possible to use an excess amount exceeding the above-mentioned range.

The method for reacting components (a), (b), and (c) is to mix predetermined amounts of the above three components and allow the reaction to occur at a temperature within a range where imidization does not substantially occur. If the above three components are not uniformly mixed, it may be preferable to use a reaction solvent to facilitate the progress of the reaction.

The temperature at which imidization does not substantially occur, which limits the reaction temperature for resin production, is generally 1, although it varies depending on the reaction time.
The temperature is 00°C or lower, more preferably 70°C to room temperature.

Note that when an amide acid group is generated by the reaction between an acid anhydride group and an amine group, heat is generated, so in order to control the internal temperature,
In some cases, external cooling may be required.

The resin (prepolymer) thus obtained is separated from the solvent when a reaction solvent is used, or is left as it is and water and a basic compound are added to obtain a coating composition.

In this case, in addition to water, a small amount of an organic solvent (which may be the same as or different from the reaction solvent) that is miscible with water may be added.

Such solvents include N-methylpyrrolidone, N,N-
Aprotic polar solvents, mainly amide solvents such as dimethylacetamide, N,N-dimethylformamide, tetramethylurea, hexamethylphosphoramide, dimethyl sulfoxide, etc., methyl cellosolve, ethyl cellosolve, tetrahydrofuran dioxane anisole, etc. , ethereal and/or alcoholic solvents, acetone,
Examples include ketone solvents such as methyl ethyl ketone and cyclohexanone, and ester solvents such as ethyl acetate.

Furthermore, as described above, water-soluble and volatile liquid glycols can be used in excess as a solvent.

Naturally, in view of the gist of the present invention, the amount of the solvent to be used is preferably small, and it is preferable to use a small amount as long as there is no problem with the reaction.

In particular, when the resin is not separated from the solvent and water and a basic compound are added thereto to form an aqueous solution, the smaller the amount, the better.

In that case, the solvent is preferably one that is miscible with water and does not produce any undesirable products upon reaction with water.

Basic compounds include ammonia water, ammonia, and trialkylamines such as triethylamine, N-alkyldiethanolamines such as N-methyldiethanolamine, and N-based compounds such as N,N-didimethylethanolamine.
, N-dialkylethanolamine, monoethanolamine, diethanolamine, triethanolamine or N,N-dimethylaniline, and mixtures thereof.

The basic compound may be added in an amount sufficient to make the resin water-soluble.

An ester-forming catalyst may also be added to promote the ester reaction during baking.

As the catalyst, a catalyst commonly used for ester production can be used, but it is preferable that it is uniformly dissolved in the water-soluble paint.

Examples of such catalysts include zinc acetate, sodium carbonate, lead naphthenate triethanolamine titanate, and titanium acetylacetate.

Further, the coating material of the present invention may contain a portion of other water-soluble resins such as water-soluble phenol resin, water-soluble amine resin, hexamethoxymethylated melamine, and water-soluble polyester resin.

Naturally, coloring agents such as pigments and dyes may be added depending on the purpose.

The paint of the present invention forms a film by conventional coating and baking, or by applying it by electroflow and baking.

The baking temperature varies depending on the composition, purpose of use, curing time, etc., but is generally in the range of 150 to 450°C.

The coating film obtained by the paint of the present invention has well-balanced practical performance in terms of hardness, flexibility, adhesion, heat resistance, chemical resistance, etc., and is suitable for electrical insulation such as wire enamel varnish and impregnated varnish. It can be used for a wide range of applications, such as protection for aluminum appliances and heating equipment, and decorative coatings.

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

The examples are illustrative and not limiting.

Example 1 148.5r of 4,4'-diaminodiphenylmethane, 3001 ethylene glycol, and 100g of glycerin were placed in a 5L three-necked flask, and then 410g of ethylene bis-(trimelitate anhydride) was gradually added under stirring, and the mixture was poured into a bath. Warm 7
React at 0°C for 2 hours.

After the reaction, 200 g of ammonia water (concentration approximately 14%) and 200 g of ion-exchanged water were added to obtain a homogeneous solution.

Then, 1.0 g of zinc acetate was added.

The solution thus obtained was diluted with ion-exchanged water to give a solution viscosity of 7.5 poise (30°C) and solid content concentration of 43.5% by weight (
An insulating coating material (dried at 200° C. for 2 hours) was obtained.

Table 1 shows the properties of an insulated wire obtained by applying this paint onto an annealed copper wire having a diameter of 1.0 mm and baking it in a conventional manner.

Example 2 158.4 g of 4,4'-diaminodiphenylmethane, 328.0 g of ethylene bis-(trimelitate anhydride), 68.8 g of benzophenone tetracarboxylic dianhydride, and N-methylpyrrolidone were placed in a 300 cc three-bottle flask. Add 300 g of the solution and react for 1 hour at a bath temperature of 50°C.

Separately, 192 g of trimellitic anhydride, 90 g of isophthalic acid, 120 g of ethylene glycol, and 55 g of glycerin were placed in a container and reacted with stirring at a bath temperature of 200 to 220° C. for 2 hours.

After the reaction, 65 g of trimethylamine and 350 g of water were added to obtain a polyester resin solution.

Next, this polyester resin solution, the previously obtained polyamic acid solution, and 172 g of triethylamine were mixed with stirring to obtain a uniform solution.

Diluted with ion-exchanged water, solution viscosity 8.0 poise (30℃)
An insulating paint having a solid content concentration of 44.1% by weight was obtained.

Table 1 shows the properties of the insulated wire obtained by applying and baking this insulating paint onto an annealed copper wire having a diameter of 1 mm in the same manner as in Example 1.

Example 3 3 equivalents of trimethic anhydride and 1.5 equivalents of ethylene glycol diacetate were mixed at 200° C. for 4 hours, and then 50 to 6
450 g of crude ethylene bis(trimellitate anhydride) obtained by reaction under reduced pressure of 0 mmHg for 8 hours, 4,4
'-Diaminodiphenylmethane 83.2g, 4,4'-
Diaminodiphenylsulfone 44.6g Tris-(β-
1040 g of hydroxyethyl isocyanurate, 50 g of ethylene glycol, and methyl cellosolve 4001 are placed in a container and reacted for 2 hours at a bath temperature of 60° C. with stirring.

After the reaction, 200 g of ammonia water (concentration: about 14%) and 200 g of water were added, and the mixture was stirred at 60° C. for 30 minutes to obtain a homogeneous solution.

2.0 g of lead naphthenate was added to this solution.

Then, it was diluted with water to give a solid content concentration of 44.1% by weight and a solution viscosity of 1.
A 1 poise insulating paint was obtained.

Table 1 shows the properties of the insulated wire obtained by applying and baking this insulating paint onto an annealed copper wire having a diameter of 1 mm in the same manner as in Example 1.

Example 4 A third 300 cc flask was charged with 9.9 g of 4,4'-diaminodiphenylmethane, 3.6 g of 2.3-hydroxypropylamine, 30 g of ethylene glycol, and 46.6 g of hexamethylene bis-(trimelitate anhydride). Stir for 2 hours at a bath temperature of 60°C.

Thereafter, 18 g of ammonia water (concentration approximately 14%), 20 g of water, and 0.1 g of lead naphthenate were added and stirred for 30 minutes at a bath temperature of 50° C. to obtain a uniform solution.

This solution was applied on a copper plate with a thickness of 0.3 mm and heated to 150°C.
After pre-drying for 30 minutes at 250°C, a coating film with a glossy surface was obtained by baking at 250°C for 5 minutes.

Further, even when this copper plate was bent, no cracks were generated in the coating film.

Example 5 Tetramethylene bis-(trimellitate anhydride) 30.
7 g, 1,2,3,4-butanetetracarboxylic dianhydride 5.9 g, 4,4'-diaminodiphenylmethane 9.
9g tris(β-hydroxyethyl)in cyanurate 7.7.8g and triethylene glycol 30.0
g in a container and stirred for 2 hours at a bath temperature of 60°C.

Thereafter, 20 g of ammonia water (concentration approximately 14%), 20 g of water, and 0.1 g of zinc acetate were added and stirred for 30 minutes at a bath temperature of 50° C. to obtain a homogeneous solution.

This solution was applied onto a copper plate with a thickness of 0.3 mm, pre-dried at 150°C for 30 minutes, and then baked at 250°C for 5 minutes, resulting in a coating film with surface brightness.

Further, even when this copper plate was bent, no cracks were generated in the coating film.

Claims (1)

[Scope of Claims] Bistrimeritate diamide represented by the formula 1(a), (wherein R represents a divalent organic group having 2 to 15 carbon atoms mainly consisting of an aliphatic hydrocarbon residue) a polycarboxylic acid component consisting mainly of anhydride (b) an amine component having at least two or more primary amine groups, and (C) at least one type of polyol compound each at a temperature at which imidization does not substantially occur; The remaining carboxyl groups are then neutralized with a basic compound to form salts to make them water-soluble.