JPS5928350B2 - Thermosetting high solids paint composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to a thermosetting high solids coating composition.

More specifically, it is characterized by containing a diester and/or monoester of an α3β-monoethylenically unsaturated dicarboxylic acid having an internal double bond, and a polymerizable monomer having a ring structure substituted with a carboxyl group and a methyl group. The present invention relates to a thermosetting high solids coating composition comprising a copolymer and an aminoplast resin. In recent years, there has been a growing demand for paint compositions to be resource-saving and pollution-free.

In particular, it is common practice to reduce the solvent content and increase the solid content in paints, since this is advantageous in that conventional manufacturing or coating equipment can be used as is.
On the other hand, amino-
Acrylic resin paint compositions have chemical resistance, solvent resistance,
It is widely used because it produces coatings with excellent weather resistance and various other mechanical properties.

However, the solid content concentration of currently used amino-acrylic resin paints at the time of application is approximately 50% by weight or less, and attempts to further increase the solidity content have resulted in the following problems.

That is, in conventional products, in order to increase the solid content concentration and avoid increasing the viscosity, it was necessary to extremely lower the molecular weight of the resin.

As a result, coating film properties such as stain resistance, corrosion resistance, chemical resistance, and hardness deteriorated, and the baking temperature also increased somewhat. Therefore, the present inventors have made extensive studies to obtain a resin solution free from the above-mentioned problems. Ester (however, Rl,
By introducing R2 into the resin (R2 is H or an alkyl group of C1 to ClO), a resin solution with a high solid content concentration and low viscosity can be obtained without drastically lowering the molecular weight of the resin. (2) and/or a polymerizable monomer having a ring structure represented by formula (3) (R3=C1 to Cl
When used in combination with O alkylene group or polymethylene group R4=H or CH2 group, the viscosity hardly increases, resulting in low viscosity and high solids content, as well as good coating performance such as hardness and stain resistance. As a result, compared to general thermosetting high solids coating compositions,
It was discovered that the coating film performance is significantly superior, and the present invention was completed.

That is, the present invention is based on the general formula (A) (1) (where Rl and R2 represent H or an alkyl group of C1 to ClO).

) Diester and/or monoester of α,β-monoethylenically unsaturated dicarboxylic acid
......5 to 50 parts by weight, relating to (4) general formula and/or.

The diester or monoester of (1) α,β-monoethylenically unsaturated dicarboxylic acid shown in general formula (1), which is the starting material for the copolymer used in carrying out the present invention, has a low viscosity of the copolymer resin. It is effective for

Rl and R2 in the general formula of the monomer have 1 carbon number
It needs to be 0 or less. If the number of carbon atoms is greater than 10, the polymerization reactivity decreases, it is difficult to obtain a copolymer resin with a uniform composition, and the viscosity also increases, which is not preferable. Also, α, β shown in general formula (1)
- The diester and/or monoester of monoethylenically unsaturated dicarboxylic acid must be copolymerized in the copolymer in an amount of 5 to 50 parts by weight. The monomer is 5
If the amount is less than parts by weight, the effect cannot be sufficiently exhibited. That is, it does not contribute to lowering the viscosity or improving the performance of the coating film. On the other hand, when the monomer is contained in an amount of 50 parts by weight or more, coating film performance such as initial adhesion, impact resistance, and chemical resistance deteriorates, which is not preferable. Specific examples of diesters or monoesters of α,β-monoethylenically unsaturated dicarboxylic acids represented by general formula (1) include diethyl maleate, dibutyl maleate, dioctyl maleate, methyl maleate, ethyl maleate, Examples include propyl maleate, hexyl maleate, isobutyl maleate, pentyl maleate, diethyl fumarate, dibutyl fumarate, dioctyl fumarate, ethyldecyl fumarate, butyl yactyl fumarate, and the like.

These may be used alone or as a mixture of two or more. In producing the copolymer shown in the third term in the present invention, a polymerizable monomer having a methyl-substituted ring structure represented by the general formula (2) or the general formula (3) is used.

This monomer can lower the viscosity of the resulting resin solution and increase the solid content compared to the case where a corresponding polymerizable monomer having a ring structure without a methyl group is used. Moreover, it is also excellent in terms of improving coating film performance in terms of hardness and stain resistance. General formula (2), (3)
It is necessary to copolymerize the polymerizable monomer having the ring structure represented by 3 to 40 parts by weight in the copolymer.

That is, when the amount of the monomer is 3 parts by weight or less, the stain resistance and hardness of the coating film decrease, and no effect on coating performance is observed due to the use of the monomer. On the other hand, if the monomer is contained in an amount of 40 parts by weight or more, coating film performance such as initial adhesion, impact resistance, and alkali resistance deteriorates, which is not preferable.
Specifically, the polymerizable monomers having a ring structure represented by general formulas (2) and (3} include methyltetrahydrophthalic anhydride, methyltetrahydrophthalic acid, methylhexahydrophthalic anhydride, methylhexahydrophthalic acid, etc. , 2-
Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate Acrylate, 5-hydroxypentyl (meth)acrylate, 6-
α,β- such as hydroxyhexyl (meth)acrylate, neopentyl glycol mono(meth)acrylate, etc.
It is a monoester of a monoethylenically unsaturated carboxylic acid with a hydroxyalkyl ester.

These may be used alone or as a mixture of two or more. (Il) used in producing the copolymer
i) The hydroxyalkyl ester of α monoethylenically unsaturated carboxylic acid needs to be copolymerized in the copolymer at a ratio of 5 to 50 parts by weight, and if the amount of the monomer is less than 5 parts by weight, When combined with a crosslinking agent such as aminoplast resin, the crosslinking density is low, resulting in poor solvent resistance, chemical resistance, etc. of the coating film.On the other hand, if the monomer exceeds 50 parts by weight, the combination with the above-mentioned crosslinking agent In this case, the crosslinking density becomes too high, resulting in poor flexibility of the coating film, which is also economically unfavorable. Specific examples of the hydroxyalkyl ester of α,β-monoethylenically unsaturated carboxylic acid used in the present invention include:
2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate
Acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate,
6-hydroxyhexyl (meth)acrylate, neopentyl glycol mono(meth)acrylate, 3-butoxy-12-hydroxypropyl (meth)acrylate,
2-Hydroxy-1-phenylethyl (meth)acrylate, polypropylene glycol mono(meth)acrylate, glycerin mono(meth)acrylate monohalf fumarate, etc., α,β-monoethyl! Examples include hydroxyalkyl esters of unsaturated carboxylic acids.

These may be used alone or as a mixture of two or more.

In the present invention, the component (lv) is used in an amount of 87 parts by weight or less when producing the copolymer.

Specific examples of the QV) components include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, etc.
, β-monoethylenically unsaturated carboxylic acids; methyl (meth)acrylate, ethyl (meth)acrylate, n
-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, s
ec-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, n
- Hexyl 2 (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, and other acrylic or methacrylic acids. Alkyl esters; N-methoxymethyl (meth)acrylamide,
N-ethoxymethyl (meth)acrylamide, N-n-
Propoxydimethyl (meth)acrylamide, N-isopropoxymethyl (meth)acrylamide, N-n-butoxymethyl 5(meth)acrylamide, N-sec-
N-alco 3-oxymethylated products of α,β-monoethylenically unsaturated carboxylic acid amides such as butoxymethyl (meth)acrylamide, N-t-butoxymethyl (meth)acrylamide, N-isobutoxymethyl (meth)atalylamide; or These N-methylolated products; in addition to the group, N,N-dimethylaminoethyl (meth)acrylate,
Glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl methacrylate, benzyl methacrylate, styrene, vinyltoluene, α-
Examples include monomers such as methylstyrene, (meth)acrylonitrile, and vinyl acetate. The above monomers may be used alone or in combination of two or more depending on the purpose and use of the coating composition. In the present invention, the former
A copolymer is obtained from the monomers dl) to 0v) by a conventional solution polymerization method.

The polymerization solvent used in the solution polymerization method is not particularly limited, but includes methanol, ethanol, n-propanol,
Alcohols such as isopropanol; ethylene glycol derivatives such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Diethylene glycol derivatives such as butyl ether; aromatic hydrocarbons such as toluene, xylol, and aromatic petroleum naphtha; esters such as methyl acetate, ethyl acetate, and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone are used. These polymerization solvents may be used alone or in an appropriate combination of two or more. Examples of the polymerization initiator used include benzoyl peroxide, t-butyl perbenzoate, t-butyl peroxide, hydroperoxide, cumene hydroperoxide, di-t-
Butyl peroxide, t-butyl peroctoate,
Examples include organic peroxides such as t-butyl perbenzoate, and azo compounds such as azobisisobutyronitrile and azodiisobutyric acid nitrile. These polymerization initiators may be used alone or in an appropriate combination of two or more.
If necessary, chain transfer agents such as dodecyl mercaptan, 2-ethylhexyl thioglycolate, carbon tetrachloride, etc. may be used to adjust the molecular weight. The weight average molecular weight of the copolymer used in the present invention is 1,000 to 30,
000, preferably from 2,000 to 10,000.

When the solid content concentration of a resin solution whose copolymer has a weight average molecular weight of 30,000 or more is increased, the viscosity increases significantly and the object of the present invention cannot be achieved. On the other hand, when the weight average molecular weight is 1000 or less, the coating film performance is not sufficient.

Next, the aminoplast resin (component (B)) used in the present invention reacts with the hydroxyl groups and carboxy groups in the copolymer when heated to form a strong film.

The aminoplast resin contains 100 parts by weight of the above copolymer (
It is used at a ratio of about 5 to 50 parts by weight (solid content). Coatings made from compositions in which the aminoplast resin is added in an amount less than 5 parts by weight per 100 parts by weight of the copolymer have insufficient crosslinking density, resulting in poor solvent resistance and resistance. Poor chemical properties. On the other hand, the resin was
A coating film obtained from a composition containing more than 0 parts by weight,
This is not preferable because the crosslinking density becomes too high and flexibility becomes poor. Specific examples of aminoplast resins include urea formaldehyde resin, melamine-formaldehyde resin, benzoguanamine-formaldehyde resin,
Examples include resinous condensates produced by reacting various triazine derivatives with formaldehyde or etherified products thereof. Incidentally, during the production of etherified products, alcohols used as etherification agents include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, 2-ethylbutanol, 2-ethylhexanol, benzyl alcohol, lauryl alcohol, etc. Alcohols having 1 to 4 carbon atoms are preferred. In the composition of the present invention, an epoxy resin may be added in combination in order to improve coating film performance such as adhesion, corrosion resistance, and mechanical properties. The amount of the epoxy resin is 30 parts by weight (solid content) or less, preferably about 5 to 2 parts by weight, based on 100 parts by weight (solid content) of the mixture of the copolymer and aminoplast resin.
It is used in a proportion of 0 parts by weight. The amount of the epoxy resin used is 3
If it exceeds 0 parts by weight, it is necessary to increase the baking temperature, which is undesirable from the standpoint of resource conservation, and furthermore, from the standpoint of weather resistance. The epoxy equivalent weight of the epoxy resin that can be used in the present invention is about 1,000 or less, and its average molecular weight is usually 1,400 or less, preferably 700 to 1
,000 range.

Examples of the epoxy resin include polyglycidyl ethers of bisphenols, polyether derivatives of polyhydric phenols, and fatty acid-modified epoxy resins. Further, in the composition of the present invention, a curing accelerator for aminoplast resins, for example, a common acid curing accelerator such as phosphoric acid, formic acid, aromatic sulfonic acid, etc. may be used.

moreover.

The composition of the present invention may optionally contain anticorrosion agents, coloring pigments,
Appropriate amounts of extender pigments and other additives are added, and then mixed and kneaded using a known kneading method such as a sand mill, ball mill, roll mill, etc., to obtain a coating composition. The composition of the present invention thus obtained can be applied to metals, such as cold rolled steel, aluminum, brass, and those metals subjected to chemical conversion treatment, by common coating methods such as roll coating, spray coating, electrostatic coating, etc. Additionally, other substrates may be coated, such as glass, asbestos, cement roofing, leather, wood, paper, textiles, etc. Then, by baking, a hard and tough coating film can be formed.

The baking is performed at a temperature of about 100°C to 200°C and a temperature of about 10 to 40°C.
Do this for minutes.

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

"Parts" or "%" are expressed as "parts by weight" or "% by weight." Example 1 Method for producing copolymer 30 parts of styrene, 20 parts of butyl acrylate, 15 parts of 2-hydroxyethyl methacrylate, 5 parts of acrylic acid,
20 parts of dibutyl fumarate, 100 parts of a monomer mixture consisting of 10 parts of a reaction product (thiester compound) of methylhexahydrophthalic anhydride and 2-hydroxyethyl acrylate, 5 parts of azobisisobutyronitrile, and t-butyl peroct. To 46 parts of ethylene glycol monoethyl ether, which is a polymerization solvent, were added 11 parts of an initiator consisting of 5 parts of t-butyl perbenzoate and 1 part of t-butyl perbenzoate, and
Polymerization was carried out at 0°C for 8 hours.

The polymerization method was a conventional dropping method, and the dropping time was 2 hours.

The properties of the obtained copolymer resin were that the nonvolatile content was 67.6%, the acid value was 32.8, and the viscosity (at 20° C.) was 19.5 Stokes. Preparation and painting of paint To 80.0 parts of the resin solution obtained by the above method, add methylated melamine resin [Nikalatsukku MS21BC, Sanwa Chemical Co., Ltd.
8) Product name: Non-volatile content 70%] 20.0 parts and 2.8 parts of a 25% solution of para-toluene sulfonic acid in ethylene glycol monobutyl ether were added to prepare a paint.

This prepared paint has a non-volatile content of 66.9% and a viscosity (20℃
) It was 16.5 Stokes.

When using this paint, use Solbetsuso #100 (trade name, manufactured by Standard Oil Co.) as a diluent,
℃, adjust food cup #4 to 40 seconds,
A zinc phosphate treated plate (0.8 x 70 x 150 ml) was hot sprayed and baked at 150°C for 20 minutes. Table 1 shows the performance results of the coating film thus obtained.

Example 2 Production of copolymer 30 parts of styrene, 15 parts of butyl acrylate, 15 parts of 2-hydroxyethyl methacrylate, 20 parts of dibutyl fumarate, reaction product of methylhexahydrophthalic anhydride and 2-hydroxyethyl acrylate ( Polymerization was carried out in the same manner as in Example 1 except that 100 parts of a monomer mixture consisting of 20 parts of monoesterified product was used in place of the monomer mixture of Example 1.

The characteristic values of the obtained resin are non-volatile content 68.0% and acid value 26.
．． 5. Viscosity (20°C) was 20.0 Stokes.

Preparation and painting of paint A paint was prepared using the same formulation method as in Example 1 using the resin solution obtained by the above method.

This prepared paint had a non-volatile content of 67.2% and a viscosity (20 C) of 15.5 Stokes.

When using this paint, use Solbetsuso #100 as a diluent, adjust it to 40 seconds at 50°C in a food cup #4, and use a zinc phosphate-treated plate (0.8 x 70 x 1
50mm) and then heated at 150℃ for 20 minutes.
It was baked for a minute. Table 1 shows the performance results of the coating film thus obtained.
Shown below.

Example 3 Production method of copolymer 30 parts of methyl methacrylate, 20 parts of butyl acrylate
15 parts of 2-hydroxyethyl methacrylate, 5 parts of acrylic acid, 20 parts of dibutyl fumarate, and 10 parts of the reaction product of methylhexahydrophthalic anhydride and 2-hydroxyethyl acrylate were added to 100 parts of the monomer mixture of Example 1. Polymerization was carried out in the same manner as in Example 1 except for using the monomer mixture.

The characteristic values of the obtained resin 5 are non-volatile content 69.0% and acid value 3.
6.9, and the viscosity (20 is C) was 17.5 Stokes.

Preparation and Coating of Coating A coating was prepared using the same formulation process as in Example 1 using the resin solution obtained by the above method.

This prepared paint had a nonvolatile content of 68.0% and a viscosity (20 C) of 13.0 Stokes.

When using this paint, use Solbetsuso #100 as a diluent, adjust it to 40 seconds at 50°C in a food cup #4, and apply it to a zinc phosphate-treated plate (10.8 x 70 x
150mm), then hot sprayed at 150℃ for 20 minutes.
It was baked for a minute. Table 1 shows the performance results of the coating film thus obtained.
Shown below.

Example 4 Production method of copolymer Styrene 29 parts, butyl acrylate 28 parts, 2-hydroxyethyl methacrylate 15 parts, acrylic acid 3 parts,
Example 1 was prepared by replacing the monomer mixture of Example 1 with 100 parts of a monomer mixture consisting of 20 parts of dibutyl maleate and 5 parts of a reaction product (monoesterified product) of methylhexahydrophthalic anhydride and 2-hydroxyethyl acrylate.
Polymerization was carried out in the same manner.

The characteristic values of the obtained resin are non-volatile content 66.5% and acid value 26.
．． 2. Viscosity (2'C) was 83 Stokes.

Preparation and coating of paint To 80.0 parts of the resin solution obtained by the above method, 20.0 parts of methylated melamine resin [Nikaratsuku MS21BC] and 7 parts of Epicoat 1001 [trade name, manufactured by Ciel (4)] were added.
5 parts of 0% xylol solution, 2 parts of para-toluenesulfonic acid
5% ethylene glycol monobutyl ether solution 2.8
and mixed the paint.

This prepared paint has a non-volatile content of 66.2% and a viscosity (2'C
) It was 7.0 Stokes. When using this paint, use Solbetsuso #100 as a diluent and adjust it to 40 seconds at 50°C with a #4 food cup, hot plate it on a zinc phosphate treated board (0.8 x 70 x 150mTn), and then Baked for 20 minutes. Table 1 shows the performance results of the coating film thus obtained.

Example 5 Production method of copolymer Styrene 29 parts, butyl acrylate 38 parts, 2-hydroxyethyl methacrylate 15 parts, acrylic acid 3 parts,
Polymerization was carried out in the same manner as in Example 1 except that the monomer mixture of Example 1 was replaced with 10 parts of dibutyl maleate and 100 parts of a monomer mixture consisting of 5 parts of the reaction product of methylhexahydrophthalic anhydride and 2-hydroxyethyl arylate. I did it.

The characteristic values of the obtained resin are non-volatile content 66.2% and acid value 24.
．． 8. Viscosity (20°C) was 9.8 Stokes. Preparation and painting of paint A paint was prepared using the same formulation method as in Example 4 using the resin solution obtained by the above method.

This prepared paint has a non-volatile content of 65.9% and a viscosity (20℃
) It was 8.0 status.

When using this paint, use Solbetsuso #100 as a diluent and adjust it to 50°C for 40 seconds in a food cup #4.
0mm) and then baked at 1500C for 20 minutes. Table 1 shows the performance results of the coating film thus obtained.

Example 6 Method for producing copolymer 2 parts of styrene, 2 parts of 2-hydroxyethyl methacrylate
7 parts, 1 part of acrylic acid, 40 parts of dibutyl fumarate, 3 reaction products (monoesterified product) of methylhexahydrophthalic anhydride and 2-hydroxyethyl acrylate
100 parts of a monomer mixture consisting of 0 parts, 5 parts of azobisisobutyronitrile, 5 parts of t-butyl peroctoate,
11 parts of an initiator consisting of 1 part of t-butyl perbenzoate was added to 46 parts of ethylene glycol monoethyl ether, which was a polymerization solvent, and polymerization was carried out at 120°C for 8 hours.

The polymerization method was a conventional dropping method, and the dropping time was 2 hours.

The properties of the obtained copolymer resin were that the nonvolatile content was 67.9%, the acid value was 43.6, and the viscosity (200C) was 23.1 Stokes. Preparation and coating of paint A paint was prepared using the same formulation method as in Example 1 using the resin solution obtained by the above method.

This prepared paint has a non-volatile content of 67.0% and a viscosity (20℃
) It was 17.3 Stokes.

When using this paint, use Solbetsuso #100 (same as Example 1) as a thinning agent, adjust it to 40 seconds at 50°C with a #4 food cup, and use a zinc phosphate-treated plate (0.8 x 70 x 150m0, and then baked at 150°C for 20 minutes.The performance results of the coating film thus obtained are shown in Table 1.Comparative Example 1 Production method of copolymer Styrene 30 parts, butyl acrylate 30 parts, 2- 15 parts of hydroxyethyl methacrylate, 5 parts of acrylic acid,
Monomer mixture 1 consisting of 20 parts of dibutyl fumarate
Polymerization was carried out in the same manner as in Example 1 except that 00 parts of the monomer mixture of Example 1 was used.

The characteristic values of the obtained resin are non-volatile content 68.4% and acid value 24.
, 5, and the viscosity (20C) was 18.0 Stokes.

Preparation and coating of paint A paint was prepared using the same formulation method as in Example 1 using the resin solution obtained by the above method.

This prepared paint has a non-volatile content of 67.5% and a viscosity of 200%.
C) It was 15.1 Stokes.

When using this paint, use Solbetsuso #100 as a diluent, adjust it to 40 seconds at 50°C in a food cup #4, and use a zinc phosphate-treated plate (0.8 x 70 x 1
Hot spray at 50 m0, then 20 at 150'C.
I baked it to a certain extent. Table 1 shows the performance results of the coating film thus obtained.
Shown below.

Comparative Example 2 Method for producing copolymer 30 parts of styrene, 30 parts of butyl acrylate, 15 parts of 2-hydroxyethyl methacrylate, 5 parts of acrylic acid,
Polymerization was carried out in the same manner as in Example 1 except that 100 parts of a monomer mixture consisting of 20 parts of 2-ethylhexyl acrylate was used in place of the monomer mixture of Example 1.

The characteristic values of the obtained resin are non-volatile content 67.6% and acid value 22.
, 8, and the viscosity (200C) was 38.4 Stokes.

Preparation and coating of paint A paint was prepared using the same formulation method as in Example 1 using the resin solution obtained by the above method.

This prepared paint had a non-volatile content of 66.9% and a viscosity (20 C) of 45.0 Stokes.

When using this paint, use Solbetsuso #100 as a diluent, adjust it to 40 seconds at 50°C in a food cup #4, and use a zinc phosphate-treated plate (0.8 x 70 x 1
It was hot-sprayed to 50m0 and then baked at 150°C for 20 minutes. Table 1 shows the performance results of the coating film thus obtained.

Comparative Example 3 Method for producing copolymer 30 parts of styrene, 20 parts of butyl acrylate, 15 parts of 2-hydroxyethyl methacrylate, 5 parts of acrylic acid,
20 parts of dibutyl fumarate, a reaction product of hexahydrophthalic anhydride and 2-hydroxyethyl acrylate (
Monomer mixture 10 consisting of 10 parts of monoesterified product
Polymerization was carried out by replacing 0 parts with the monomer mixture of Example 11.

The characteristic values of the obtained resin are non-volatile content 68.9% and acid value 34.
．． 7. Viscosity (2'C) was 35.0 Stokes. Preparation and coating of paint A paint was prepared using the same formulation method as in Example 1 using the resin solution obtained by the above method.

This prepared paint has a non-volatile content of 67.9% and a viscosity (2'C
)26.

It was 0 strokes.

When using this paint, use Solbetsuso #100 as a diluent, adjust it to 40 seconds at 50℃ in a food cup #4, and use a zinc phosphate-treated plate (0.8 x 70 x 15
0 mm) and then baked at 150°C for 20 minutes. Table 1 shows the performance results of the coating film thus obtained.

Claims (1)

[Claims] 1(A)(i) General formula R_1-O-CO-CH=CH-CO-O-R_2...
......(1) (However, R_1 and R_2 are H or C_1
~C_1_0 represents an alkyl group. ) Diester and/or monoester of α,β-monoethylenically unsaturated dicarboxylic acid...
...5 to 50 parts by weight, (ii) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼…………(2) and/or▲There are mathematical formulas, chemical formulas, tables, etc.▼…………( 3) (However, R_3 is an alkylene group or polymethylene group of C_1 to C_1_0, and R_4 is H or CH_3 group.) A polymerizable monomer having a ring structure represented by...
...3-40 parts by weight, (iii) hydroxyalkyl ester of α,β-monoethylenically unsaturated carboxylic acid…5-50 parts by weight, and (iv) α,β-monoethylenically unsaturated carboxylic acids,
Alkyl esters of (meth)acrylic acid, N-alkoxymethylated products of α,β-monoethylenically unsaturated carboxylic acid amide or N-methylolated products thereof, N,
N-dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)
At least one copolymerizable monomer selected from the group of acrylate, phenyl methacrylate, benzyl methacrylate, styrene, vinyltoluene, α-methylstyrene, (meth)acrylonitrile, and vinyl acetate: 87 parts by weight or less 100 parts by weight of the obtained copolymer having a weight average molecular weight of 1,000 to 30,000,
(B) consisting of 5 to 50 parts by weight of aminoplast resin;
Thermosetting high solids coating composition.