JPS62167367A - Coating composition containing novel three-dimensionally crosslinked resin particle - Google Patents

Abstract

PURPOSE:To provide the titled composition composed of a film-forming polymer, a volatile organic liquid diluent and a specific three-dimensionally crosslinked resin, having excellent coatability and storage stability and giving a high-quality coating film. CONSTITUTION:The objective composition is composed of (A) a film-forming polymer such as acrylic resin, (B) a volatile organic liquid diluent capable of dissolving or dispersing the component A and (C) particles of a three- dimensionally crosslinked resin (preferably a condensed resin such as polyester resin or a polymerized resin such as acrylic resin) insoluble but stably dispersible in a combination of the components A and B, having an average particle diameter of 0.01-10mu and having a group of formula (Y is -CONH-, -COO- or -CO-).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a coating composition, and more particularly to a coating composition containing resin particles that has excellent coating workability and storage stability and can provide a high-quality coating film. .

Conventional technology So-called high-solid paints, in which three-dimensional resin particles called microgels are dispersed in a paint composition containing a resin vehicle, are attracting attention in the field of painting automobiles, home appliances, etc. due to their workability and coating performance. Many proposals have been made regarding methods for producing microgel particles, methods for dispersing microgels, etc. However, in conventional paints, the storage stability and coating workability of the paint composition have only been pursued together with the film performance, and resins have not been used in the paint film-forming process, baking process, etc. Particle aggregation and the resulting deterioration of the appearance of the coating film have tended to be overlooked as unavoidable to some extent in the technology of incorporating resin particles. Now, the three-dimensional resin particles that have been proposed so far either have no functional groups, or even if they do have functional groups, the types of them are limited to carboxyl groups, hydroxyl groups, and amino groups. This is mainly due to consideration of crosslinking reactions, pigment dispersibility, etc. when blending aminoplasts and block polyisocyanate compounds as crosslinking agents into coating compositions, or the compatibility of monomers in the production of coating resins. This is thought to be due to the solubility in solvents. In fact, monomers with bonds such as urea and urethane have high crystallinity and are difficult to handle because they are difficult to dissolve in other monomers or solvents. To date, there have been no reports of three-dimensional resin particles using such monomers. It has not been.

In addition, urea, urethane, etc. are described by Burn in J.

It is a group with high molecular cohesive energy of an atomic group reported in Chim, Phys. In reality, from the viewpoint of stable dispersion of resin particles in the resin, it has been considered undesirable and has not been considered.

The present inventors conducted research on three-dimensional resin particles having atomic groups with high molecular cohesive energy, and found that when they coexist with other resins, solvents, etc., extremely specific interfacial interactions occur. It also has the property of easily dissociating due to thermal energy, etc. even if it aggregates or aggregates.
The present inventors realized that the present invention is extremely desirable in terms of dispersion stability, coating appearance, etc., and thus completed the present invention.

Problems to be Solved by the Invention Accordingly, the object of the present invention is to provide a high-solid paint that has good coating workability and storage stability, and has particularly excellent film appearance and workability in terms of film formation and baking. An object of the present invention is to provide a coating composition capable of providing a coating film having intermediate coating film gloss and sharpness.

Means for Solving the Problems According to the present invention, the above object is achieved by using a film-forming polymer (A).
, a volatile organic liquid diluent (B) that dissolves or disperses the polymer, and a volatile organic liquid diluent (B) that is insoluble and stably dispersed in the combination of the polymer and the diluent and has an average particle size of 0.01 to 10 μm.
This can be achieved by a coating composition comprising three-dimensional resin particles (C) having a group represented by the formula 1 (where Y is -CONH- and -Coo-Alui is -C○-).

The film-forming polymer (A) used in the present invention is usually any film-forming polymer used in solvent-based coatings, such as acrylic resin, alkyd pine resin,
Oil-free polyester resin, epoxy resin, or modified resin thereof, which may have functional groups such as hydroxyl groups and carboxyl groups.1 Normally acid value is 0.5 to 6.
0, hydroxyl value 20-200, number average molecular weight 5°O
~10,000, but can be arbitrarily selected from a wide variety of types as long as it is soluble or dispersible in a solvent and has film-forming ability.

The above film-forming polymer can be dissolved or dispersed in the diluent (B).

It can also exist partially dissolved or partially. In this case, volatile organic liquids are used, typically aromatic hydrocarbons such as toluene, xylene,
Various petroleum fractions containing aromatics; esters such as butyl acetate, ethylene glycol diacetate, 2-ethoxyethyl acetate, etc.; ketones such as acetone, methyl isobutyl ketone, etc.; alcohols such as butyl alcohol; aliphatic hydrocarbons or mixtures thereof; can give.

The coating composition of the present invention includes the above-mentioned film-forming polymer,
Furthermore, the most characteristic part of the volatile organic liquid diluent system is that special new polymer fine particles are stably dispersed therein. This polymer fine particle (C) has an average particle diameter of 0.0
H is within the range of 1 to 10μ, and 1 set 1 (However, Y is -CONH-1N-
These are three-dimensional resin particles having a group represented by Y--C○0- or 100-). The resin type may be any of condensation resins such as polyester resins, alkyd resins, epoxy resins, and melamine resins, and polymerization resins such as acrylic resins.

Such resin particles can be conveniently manufactured by various well-known techniques, as described in the patent application entitled "Three-Dimensional Resin Particles" filed by the same applicant on the same date as the present application. Namely.

For example, the three-dimensional acrylic resin particles N-Y- having a group represented by the formula
- Copolymerizing α, β-ethylenically unsaturated monomers alone or other copolymerizable monomers by emulsion polymerization or NAD polymerization, and at this time, crosslinkable monomers having two or more ethylenically unsaturated bonds are used. It is possible to make it three-dimensional by making it exist. Alternatively, it can be advantageously produced by obtaining a three-dimensional acrylic resin having a hydroxyl group by a conventional method, reacting it with an organic isocyanate, and, if desired, reacting the reaction product with a monoalcohol or monoamine. Alternatively, at least a portion of the three-dimensional resin particles at the lower right side is a polymerizable monomer having 1 group. solution polymerization of monomer(s),
It can also be obtained as a composite resin particle consisting of a three-dimensional resin particle main body and a group of many linear polymers, some of which penetrate into the particle main body and the remaining parts extend outward from the main body.

The three-dimensional polyester resin or alkyd resin particles having the group 1 of formula 1, for example, a urethane or N-Y-urea group, can be modified with, for example, an alkyd resin having an unsaturated fatty acid group, or maleic anhydride, allyl glycidyl ether or glycidyl methacrylate. A three-dimensional resin is obtained by dispersing an alkali-neutralized polyester resin having polymerizable unsaturated groups in water in the presence or absence of an emulsifier, adding styrene and a radical initiator, and heating. , is conveniently produced by drying the resin particles, optionally pulverizing them, dispersing them in an organic solvent without active hydrogen, reacting them with an isocyanate compound, or further reacting them with a primary or secondary amine. .

In the production of melamine resin particles having urethane or urea groups, first, three-dimensional melamine resin particles are
Manufactured using the self-condensation reaction of methylol groups in melamine resin. For example, three-dimensional melamine resin particles can be obtained by dispersing a melamine resin with a high content of methylol groups in water in the presence of an appropriate emulsifier, adding a catalyst, and heating. Dry these three-dimensional melamine resin particles,
Grind and disperse in an organic solvent without active hydrogen.

isocyanate compound, or further primary or secondary
Melamine resin particles having urethane or urea groups can be produced by reacting with a grade amine.

In the production of epoxy resin particles having urethane or urea groups, three-dimensional epoxy resin particles are
It is produced by reacting a polyfunctional epoxy resin having two or more epoxy groups with an amine or amide having two or more primary or secondary amino groups in the molecule.

For example, using a polyfunctional epoxy resin in the presence of an appropriate emulsifier,
Three-dimensional epoxy resin particles are obtained by dispersing in water and reacting with a polyfunctional amine. Next, the three-dimensional epoxy resin particles are dried, pulverized, dispersed in an organic solvent without active hydrogen, and reacted with an isocyanate compound or further with IR or a secondary amine to form urethane or urea groups. Epoxy resin particles can be produced.

Examples of the isocyanate compound include organic monoisocyanates such as butyl isocyanate, stearyl isocyanate, phenyl isocyanate, and cyclohexyl isocyanate; tetramethylene-1,4-diisocyanate, and hexamethylene-1,6-diisocyanate. Organic diisocyanates such as isocyanate and isophorone diisocyanate are suitably used, and various organic amine compounds well known to those skilled in the art are suitably used as the primary and secondary amines, and the three-dimensional structure carrying one group of the present invention is preferably used. Resin NY − particles are produced.

In the present invention, as described above, N-Y having 1 group
- Three-dimensional resin particles are obtained as fine particles with an average particle size of 0.01 to 10 μ due to the manufacturing method or by a crushing treatment after manufacturing, and these are uniformly distributed in the above-mentioned film-forming polymer and diluent system. It is dispersed and contained in.

As already mentioned, the three-dimensional N-Y with one group
- Polymerized resin particles have the above-mentioned groups, i.e., urethane, urea, or amide groups, which have high molecular cohesive energy, so they have a substance-supporting function and have a large interfacial interaction between one particle and the solvent, and between the particles and the film-forming polymer. Therefore, in the solvent-film-forming polymer system, the dispersion stability of the particles themselves becomes good, and therefore the coating workability is improved. Furthermore, during film formation, particles associate and agglomerate, but thermal energy easily dissociates them into primary particles. Excellent gloss.

It can provide a smooth coating film. Therefore, it is particularly preferable that the coating composition of the present invention contains a curing agent such as aminoplast or polyvalent isocyanate, although this is not necessarily an essential component, and is used as a baking-type coating.

The present inventors further found that the characteristics of such three-dimensional resin particles are remarkable when they contain a group represented by the formula 1 at 1×10°3 mol or more per 1N-Y-00 g of the resin particle, and that the characteristics of the three-dimensional resin particles are remarkable when the group represented by the formula It has also been found that when the substituent adjacent to the N-Y- group is a phenyl group or an alkyl group having an OH group, further improvement in coating film appearance (gloss, sharpness, etc.) can be obtained. .

As described above, the coating composition of the present invention has excellent dispersion stability and coating workability in either the room-temperature drying type or bake-curing type, and also has excellent coating film appearance, especially gloss, smoothness, and This is a coating composition that is particularly superior to conventional products in terms of image clarity.

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

Reference Example 1 134 parts of bishydroxyethyl taurine, 130 parts of neopentyl glycol, and azelaic acid were added to a 2Q Kolben equipped with a stirrer, a nitrogen inlet tube, a temperature control device, a condenser, and a decanter. 236 parts of phthalic anhydride, 186 parts of phthalic anhydride, and 27 parts of xylene are charged, and the temperature is raised.Water produced by the reaction is azeotroped with xylene and removed.

The temperature was raised to 190°C over about 2 hours from the start of refluxing, stirring and dehydration were continued until the acid value equivalent to carboxylic acid reached 145, and then the mixture was cooled to 140°C.

Next, the temperature was maintained at 140°C, and "Cardura E10"
314 parts of persatic acid glycidyl ester (manufactured by Shell) were added dropwise over 30 minutes, and stirring was continued for 2 hours to complete the reaction. The resulting polyester resin had an acid value of 59, a hydroxyl value of 90, and an Mn of 1054 t''.

Reference Example 2 Production of monomer having one group on the top 155 parts of isocyanatoethyl methacrylate (manufactured by Dow Chemical Company) was charged into a 500 m12 reaction vessel equipped with a stirrer, a cooler, and a temperature control device, and the temperature was adjusted to 20°C while stirring.
While maintaining the temperature at After confirming that the absorption had disappeared, chloroform was removed by drying under reduced pressure to obtain a hexamer having a urea group.

Reference Example 3 Production of a monomer having a urea group Using the same reaction apparatus as in Reference Example 2, 155 parts of isocyanatoethyl methacrylate was charged, and the stirring temperature was set at 20°C.
61 parts of 2-amino-1-ethanol while maintaining
A mixture of 0.2 parts of hydroquinone monomethyl ether and 65 parts of chloroform was added dropwise over 15 minutes, and after stirring for another 30 minutes, -N
After confirming that the absorption of C○ groups had disappeared, chloroform was removed by drying under reduced pressure to obtain a monomer having a urea group.

Reference Example 4 Production of a monomer having a urethane group Using the same reaction apparatus as in Reference Example 2, 155 parts of isocyanatoethyl methacrylate and 0 parts of dibutyltin dilaurate were added.
．． 2 parts, 0.2 parts of hydroquinone monomethyl ether,
Add 108 parts of benzyl alcohol and raise the stirring temperature to 8.
The temperature was raised to 0° C. and held for 2 hours, and after confirming with an infrared spectrophotometer that the absorption of the -NC◯ group had disappeared, a 7-mer having a urethane group was obtained.

Reference Example 5 Production of a monomer having a urethane group Using the same reaction apparatus as in Reference Example 2, 130 parts of 2-hydroxyethyl methacrylate, 0.2 part of hydroquinone monomethyl ether, 0.2 part of dibutyltin dilaurate,
119 parts of phenyl isocyanate was charged, the stirring temperature was raised to 80°C and held for 2 hours, and after confirming with an infrared spectrophotometer that the absorption of the -NGO group had disappeared, the monomer having a urethane group was added. Obtained.

Reference Example 6 Preparation of fine resin particles: 245 parts of deionized water, 15 parts of the emulsifier having a zwitterionic group obtained in Reference Example 1, and 1 part of dimethylethanolamine were placed in an IQ reaction vessel equipped with a stirrer, a cooler, and a temperature control device.
．． Add 5 parts of azobiscyanovaleric acid to 20 parts of deionized water and 0.7 parts of dimethylethanolamine, and add 35 parts of styrene and ethylene glycol dichloromethane. A mixed solution consisting of 35 parts of methacrylate and 30 parts of n-butyl acrylate was added dropwise over a period of 60 minutes, followed by an additional 90 parts of n-butyl acrylate.
After stirring for a minute, the average particle size was 9 with a non-volatile content of 30%.
A fine resin particle dispersion of 0 mμ was obtained.

This dispersion was spray-dried to obtain fine resin particles.Reference Example 7: Preparation of ``Koju II'' particles. 15 parts of the emulsifier having zwitterionic groups obtained in Example 1 and 1 part of dimethylethanolamine
．． Add 5 parts of azobiscyanovaleric acid to 20 parts of deionized water and 0.7 parts of dimethylethanolamine, and add 35 parts of styrene and ethylene glycol dichloromethane. A mixed solution consisting of 35 parts of methacrylate, 26 parts of n-butyl acrylate, and 4 parts of the urea group-containing monomer obtained in Reference Example 2 was added dropwise over a period of 60 minutes, and then stirring was continued for an additional 90 minutes. A minute resin particle dispersion having an average particle diameter of 90 mμ as determined by laser light scattering was obtained at a concentration of 30%.

This dispersion was spray-dried to obtain fine resin particles having urea groups.

Reference Example 8 Preparation of fine resin particles: Into an IQ reaction vessel equipped with a stirrer, a cooler, and a temperature control device, 245 parts of deionized water, 15 parts of the emulsifier having a zwitterionic group obtained in Reference Example 1, and 1 part of dimethylethanolamine were added.
．． Add 5 parts of azobiscyanovaleric acid to 20 parts of deionized water and 0.7 parts of dimethylethanolamine, and add 35 parts of styrene and ethylene glycol dichloromethane. A mixed solution consisting of 35 parts of methacrylate, 26.7 parts of n-butyl acrylate, and 3.3 parts of the urea group-containing monomer obtained in Reference Example 3 was added dropwise over 60 minutes.

After that, after continuing stirring for another 60 minutes, the non-volatile content was 30%.
Thus, a fine resin particle dispersion having an average particle diameter of 92 mμ as determined by laser light scattering was obtained.

This dispersion was spray-dried to obtain fine resin particles having urea groups.

Reference Example 9 In a small IQ reaction vessel equipped with a stirrer, a cooler, and a temperature control device, 245 parts of deionized water, 15 parts of the emulsifier having natural ionic groups obtained in Reference Example 1, and 1 part of dimethylethanolamine were added.
．． Add 5 parts of azobiscyanovaleric acid to 20 parts of deionized water and 0.7 parts of dimethylethanolamine, and add 35 parts of styrene and ethylene glycol dichloromethane. A mixed solution consisting of 35 parts of methacrylate, 26 parts of n-butyl acrylate, and 4 parts of the urethane group-containing monomer obtained in Reference Example 4 was added dropwise over a period of 60 minutes, and then stirring was continued for an additional 90 minutes. At a concentration of 31%, a fine resin particle dispersion having an average particle diameter of 90 mμ as determined by laser light scattering was obtained.

This dispersion was spray-dried to obtain fine resin particles having urethane groups.

Reference Example 10 Micro resin particles 490 parts of deionized water, 30 parts of the emulsifier having amphoteric ionic group obtained in Reference Example 1, and 3 parts of dimethylethanolamine were placed in an IQ reaction vessel equipped with a stirrer, a cooler, and a temperature control device.
2 parts of 7zobiscyanovaleric acid dissolved in 40 parts of deionized water and 1.4 parts of dimethylethanolamine, 70 parts of methyl methacrylate, and ethylene glycol. 70 parts of dimethacrylate, and 5 parts of n-butyl acrylate
A mixed solution consisting of 2.4 parts and 7.6 parts of the urethane group-containing monomer obtained in Reference Example 5 was added dropwise over a period of 60 minutes, after which stirring was continued for an additional 90 minutes, and the non-volatile content was 30%. A fine resin particle dispersion having a light scattering average particle diameter of 90 mμ was obtained.

This dispersion was spray-dried to obtain fine resin particles having urethane groups.

Reference Example 11 237 parts of deionized water, 15 parts of the emulsifier having a zwitterionic group obtained in Reference Example 1, and 1 part of dimethylethanolamine were placed in a 1Ω reaction vessel equipped with a stirrer, a cooler, and a temperature control device.
．． 5 parts of azobiscyanovaleric acid was dissolved in 20 parts of deionized water and 0.7 parts of diethylethanolamine, and 1.1 parts of acrylamide was added to the solution. A solution dissolved in 8 parts of ionized water, and 35 parts of styrene, 35 parts of ethylene glycol dimethacrylate, and 28.9 parts of n-butyl acrylate.
of the mixture was added dropwise over a period of 60 minutes, after which stirring was continued for an additional 60 minutes.

Non-volatile content is 30% and the average particle size by laser light scattering is 9.
A fine resin particle dispersion having an amide mass of 0 mμ was obtained.

This dispersion was spray-dried to obtain fine resin particles having an amide group.

Reference Example 12 Production of acrylic resin varnish 800 parts of xylene and 100 parts of n-butanol were charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, an N2 gas introduction tube, and a dropping funnel, and the mixture was heated while introducing N2 gas. While heating and maintaining the temperature at 120°C, a mixture having the following composition was added dropwise from the dropping funnel at a constant rate over 3 hours.

Styrene 300 parts 2-ethylhexyl methacrylate 400 parts 2-ethylhexyl acrylate 107 parts 2-hydroxyethyl methacrylate 162 parts methacrylic acid
31 parts azobisisonitrile 20
30 minutes after completion of the addition, 3 parts of a mixture of 5 parts of t-butylperoxy-2-ethylhexanoate and 100 parts of xylene was added.
The mixture was added dropwise at a uniform rate over a period of 0 minutes. After completion of the dropping, the mixture was aged for 1 hour and 30 minutes, and then cooled to obtain an acrylic resin varnish with a non-volatile content of 50%.

Reference example 13 Acrylic varnish.

8S parts of xylene and 100 parts of n-butanol were placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, an N2 gas inlet tube, and a dropping funnel, and the temperature was raised while introducing N8 gas and maintained at 120°C. While doing so, a mixture having the following composition was added dropwise from the dropping funnel at a constant rate over a period of 3 hours.

Styrene 300 parts 2-ethylhexyl methacrylate 400 parts 2-ethylhexyl acrylate 107 parts 2-hydroxyethyl methacrylate 162 parts methacrylic acid
31 parts Monomer having urethane group obtained in Reference Example 4 50 parts Azobisisobutyronitrile 20 parts 30 minutes after completion of dropping, a mixed solution of 5 parts t-butylperoxy-2-ethylhexanoate and 100 parts xylene was added dropwise at a uniform rate over 30 minutes. After the completion of 0 drops, the mixture was aged for 1 hour and 30 minutes, and then cooled to obtain an acrylic resin varnish having urethane groups with a non-volatile content of 50%.

Reference Example 14 Acrylic varnish 850 parts of xylene and 100 parts of n-butanol were charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, an N2 gas introduction tube, and a dropping funnel, and the temperature was raised while introducing N2 gas. While maintaining the temperature at 120° C., a mixture having the following composition was added dropwise from the dropping funnel at a constant rate over 3 hours.

Styrene 300 parts 2-ethylhexyl methacrylate 400 parts 2-ethylhexyl acrylate 107 parts 2-hydroxyethyl methacrylate 162 parts methacrylic acid
31 parts Urea group-containing monomer 5 obtained in Reference Example 2
0 parts azobisisobutyronitrile 20 parts 30 minutes after completion of dropping, a mixed solution of 5 parts of t-butylperoxy-2-ethylhexanoate and 100 parts of xylene was added dropwise at a constant rate over 30 minutes. After the dropwise addition was completed, the mixture was aged for 1 hour and 30 minutes, and then cooled to obtain an urea group-containing acrylic resin varnish with a nonvolatile content of 50%.

Reference Example 15 Polyester Varnish The following raw materials were charged into a container equipped with a stirrer, a temperature control device, and a decanter, and heated while stirring.

Ethylene glycol 39 parts Neopentyl glycol 130 parts Azelaic acid
236 parts phthalic anhydride
186 parts xylene
30 parts Heating was continued until the acid value reached 150 while removing water produced as the reaction proceeded by azeotroping with xylene. Thereafter, the temperature was cooled to 140° C., and 314 parts of Cardura E-10 (epoxy resin, manufactured by Shell Co., Ltd.) was added, and stirring was continued for 2 hours to complete 9 reactions. The resulting resin had an acid value of 9, a hydroxyl value of 90°, and a number average molecular weight of 1,050. This resin was diluted with xylene to a nonvolatile content of 60% to obtain a polyester resin varnish having a Gardner viscosity of Y.

Reference Example 16 Polyester Varnish 1667 parts of the polyester resin varnish obtained in Reference Example 15, 1 part of dibutyltin dilaurate, and 25 parts of phenyl isocyanate were placed in a reaction vessel equipped with a stirrer, a cooler, and a temperature control device.
and 16 parts of xylene, and stirred at a temperature of 120
The temperature was raised to ℃, held for 1 hour, and measured using an infrared spectrophotometer.
After confirming that the absorption of NGO groups has disappeared, the solid content is reduced to 6
A polyester resin varnish having 0% urethane groups was obtained.

Example 1 20 parts of the fine resin particles having urea groups obtained in Reference Example 7 were mixed with 42 parts of xylene, 30 parts of methyl isobutyl ketone, and n-
Dispersed in 8 parts of butanol. While stirring this with a disper, 280 parts of the acrylic resin varnish obtained in Reference Example 12 and 120 parts of butylated melamine (Niepan 208E-60, manufactured by Mitsui Toatsu Chemical Co., Ltd.) were mixed to obtain a clear paint. Adjust the spray viscosity of this paint using xylene #4
Ford Cup (25 seconds) was applied to a vertically erected tin plate using an air spray gun to a film thickness of approximately 40 parts. After leaving it for 5 minutes, it was baked at 140° C. for 25 minutes to obtain a coating film.

The PGD value of the coating film was 0.9, and the visual smoothness was excellent.

In addition, the PGD value is Portable distinct.
Ess of Image Grossmeter (N
This value indicates the sharpness of the image, and the larger the value, the better the image quality.

Examples 2 to 9 In Example 1, with the formulation as shown in the table below, Reference Example 7
A coating film was obtained in exactly the same manner except that the fine resin particles, organic solvent, and melamine resin obtained in Steps 1 to 11, and the acrylic resin or polyester resin of Reference Examples 12 to 16 were used. The PGD values and smoothness of those coatings are shown in the table.

Comparative Example 1 In Example 1, the micro resin particles having no urea or urethane group from Reference Example 6 were used as micro resin particles instead of the micro resin particles having a urea group from Reference Example 7 with the formulation as shown in the table below. A coating film was obtained using the same formulation and method except for the following.

The PGD value and visual smoothness of the coating film are shown in the table.

Comparative Example 2 In Example 6, the fine resin particles having no urea or urethane group of Reference Example 6 were used instead of the fine resin particles having a urea group of Reference Example 8 as fine resin particles with the formulation as shown in the table below. Other than that, a coating film was obtained using the same formulation and method.

The PGD value and visual smoothness of the coating film are shown in the table.

(Margin below)

Claims (6)

[Claims] (1) A film-forming polymer (A), a volatile organic liquid diluent (B) for dissolving or dispersing the polymer, and a combination of the above polymer and diluent that is insoluble and stably dispersed. A three-dimensional resin with an average particle size of 0.01 to 10μ and a group represented by the formula ▲Mathematical formula, chemical formula, table, etc.▼ (However, Y is -CONH-, -COO- or -CO-) A coating composition comprising particles (C). (2) The composition according to claim 1, wherein the three-dimensional resin particles are composed of a condensed resin such as a polyester resin and a polymerized resin such as an acrylic resin. (3) The composition according to claim 1, wherein the film-forming polymer is an acrylic resin, an alkyd resin, an oil-free polyester resin, an epoxy resin, or a modified resin thereof. (4) Resin solid content in weight ratio of film-forming polymer (A
) 50-99.5 parts to three-dimensional resin particles (C) 50-0
．． A composition according to any one of claims 1 to 3 comprising 5 parts. (5) The composition according to claim 1, wherein the organic liquid diluent is selected from aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, ethers, ketones and esters. (6) The composition according to claim 1, which contains an aminoplast or a polyisocyanate crosslinking agent.