JPH01242669A - Coating composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in a capability of forming a high-solid coating and sag resistance and improved in the smoothness, toughness and appearance of a film, by mixing a film-forming polymer having a functional group reactive with a crosslinking agent with a volatile organic liquid diluent, specified fine polymer particles and a crosslinking agent. CONSTITUTION:A polymer component is obtained by mixing 50-99.5wt.% film- forming polymer (A) having a functional group reactive with a crosslinking agent, such as an acrylic (co)polymer having a number-average MW of 1000-10000 and a side chain of formula I (wherein n is 3-50), with 50-0.5 pt.wt. fine polymer particles (B) obtained by copolymerizing at least two alpha,beta- ethylenically unsaturated monomers in an aqueous or organic solvent in the presence of a resin having a group of formula II [wherein R is a (substituted) 1-6C alkylene or phenylene, and Y is COOH or SO3OH] and being insoluble but stably dispersible in a combination of component A with component C. 100 pts.wt. obtained polymer component is mixed with 5-100 pts.wt. crosslinking agent (C) such as aminoplast resin, and 10-2000 pts.wt. organic volatile liquid diluent (D) for carrying component A per 100 pts.wt. total of components A, B and C.

Description

[Detailed Description of the Invention] Technical Field The present invention relates to a coating composition, and more particularly to a coating composition containing crosslinked copolymer particles useful as an automotive or other decorative coating. .

Conventional Technology Solvent-type coating compositions containing a binary C film-forming polymer, an organic solvent, and a crosslinking agent as main components and using a curing catalyst as necessary are widely used for automobiles, home appliances, decorative items, etc. However, in the case of darkening paints, there are always problems with workability, finished appearance such as smoothness of the coating film, gloss, and various desired physical properties.

It is particularly important to increase the solids content of coating compositions.For example, in the case of automotive coatings, in the case of polyester resins, it is necessary to reduce the molecular weight of the resin or incorporate so-called soft I-monomers. Accordingly, those containing resin in a volumetric solid content ratio (VolNV) of about 50 to 52% are used. However, the conventional technology has reached its limit in producing high solids, and further increasing the solid content deteriorates the appearance and film performance, making it unsuitable for automotive paints. On the other hand, in the case of acrylic resins, it is intended to make them highly solid by reducing the number average molecular weight to about 1,000 to 2,000 or by lowering the glass transition temperature. 50%, 40 to 45 with color base paint
The upper limit is approximately %, and increasing solidity higher than this is considered inappropriate because of deterioration in coating film performance. Furthermore, attempts have been made to blend polyester resins or acrylic resins with other low-viscosity polymers, but not only are they unable to achieve a very high volumetric solids ratio, but they also fail to achieve the desired results due to problems such as compatibility and poor coating performance. have not achieved their objectives.

Therefore, it is possible to achieve a much higher solidity than conventional paints, and it has excellent paint film appearance and film performance, making it a useful top coat for automobiles, home appliances, etc.! In response to this problem, the present inventors have conducted intensive research and found that the side chain represented by the formula % (where n is a real number from 3 to 50) number average molecule of 11,000~・-]
I found out that a coating composition using an acrylic polymer or copolymer of -0000 as a film-forming resin, an organic liquid diluent, a crosslinking agent, and optionally a curing catalyst meets the above purpose, A patent application was filed on the same date as the present application under the title of the invention [Coating Composition J (Patent Application (1))].

The coating composition according to the above application uses an acrylic resin composition with low viscosity, high crosslinking reactivity, and high elasticity as a film-forming resin as the main resin component, and therefore has a much higher solids content than conventional solvent-based coating compositions. When a coating composition with a large amount of water is obtained and is formed into a coating film, it can provide a coating film with excellent appearance and film properties, but in the coating line, the solid content is further increased and used as an intermediate top coat. There is a need for a high-solid paint with good workability, film properties, and finished appearance without the risk of sagging problems.

Problems to be Solved by the Invention Therefore, we have developed a high-solid paint that does not cause sagging and is particularly excellent in terms of workability, and has excellent appearance and film properties as an intermediate top coat for automobiles that is coated in a thicker film. There is a need for a coating composition that can provide an excellent coating film, and it is an object of the present invention to meet this problem.

Means for Solving the Problems According to the present invention, the object of the invention is to provide a film-forming polymer (-) having a functional group capable of reacting with a crosslinking agent, and a volatile organic liquid diluent supporting the polymer. CB>, polymer fine particles insoluble and stably dispersed in the combination of the polymer and diluent (C), and a crosslinking agent dissolved in the diluent (D>), and the above-mentioned The polymer fine particles (C) have a group in the molecule represented by the formula % (wherein R is a C1 to C6 alkylene or phenylene group that may have a substituent, and Y is -C00I+ or -5o3H). It is a crosslinked copolymer fine particle obtained by copolymerizing two or more monomers having α,β-ethylenically unsaturated groups in an aqueous or organic medium in the presence of a resin having a film-forming polymer. The number average molecular weight is 1000 to 100 and has a side chain represented by the formula % (in the formula, n is a real number from 3 to 50).
This can be achieved using a coating composition characterized by being a 00 acrylic polymer or copolymer.

BACKGROUND ART Today, in automobile painting and other fields, it is widely practiced to use coating compositions that have improved coating workability by dispersing crosslinked polymer fine particles called microgels to achieve high solidity.

However, emulsifiers, surfactants, and the like are usually required for the production of microgels or their dispersion in paints, and these have an adverse effect on coating film performance, so various proposals have been made to solve this problem. The applicant first developed a film-forming polymer (
A), a volatile organic liquid diluent (B) supporting the polymer;
), a high solid coating composition comprising polymer fine particles (C) insoluble and stably dispersed in the combination of the polymer and diluent and a crosslinking agent (D) dissolved in the diluent. , the above polymer fine particles (C) have the formula % in the molecule (wherein R is C, which may have a substituent, a ~C6 alkylene or phenylene group, Y is -COOH or -5o3)1) Using crosslinked copolymer fine particles obtained by copolymerizing two or more monomers having α, β-ethylenically unsaturated groups in an aqueous or organic medium in the presence of a resin having a group represented by We discovered that this product was extremely useful in terms of workability and coating performance, and we wanted to apply for a patent.
No. 8-129066).

In the present invention, we have focused on the fact that the polymer fine particles of the above invention are unique as resin fillers that do not adversely affect coating performance, and have developed a novel acrylic resin composition with low viscosity and high crosslinking reactivity. By combining with the coating composition of the above patent application (1) used as a film-forming resin,
This product provides a new coating composition that can provide a coating film with significantly improved workability such as sagging resistance, excellent coating appearance and physical properties, and is extremely excellent as both an intermediate coating and a top coating for automobiles. It can be said that the coating composition

The film-forming polymer (^) used in the present invention is:
A novel acrylic polymer or copolymer having a characteristic side chain represented by the formula % (wherein n is a real number from 3 to 50), which was synthesized for the first time by the inventors by the following method. That is, first of all (meta)
A method in which tetrahydrofuran is ring-opening polymerized using an acrylic acid halide and a Lewis acid metal salt, and the polymerization reaction is stopped with water, an aqueous alkali solution, or quaternary ammonium hydroxide, or a method in which tetrahydrofuran is ring-opening polymerized with a strong protic acid, and (meth) Either a method of stopping the polymerization reaction with an acrylic acid metal salt or a (meth)acrylic acid amine salt is used, and the polymerization reaction is expressed by the formula % (wherein R is hydrogen or a methyl group; n is a real number from 3 to 50). A monomer containing a terminal hydroxyl group having a repeating unit of oxytetramethylene is prepared, and 20 to 100 mol% of the monomer and 80 to 0 mol% of other α,β-ethylenically unsaturated monomers are prepared. Polymerization is carried out according to a conventional method to obtain a resin composition having a number average molecular weight of 1,000 to too much, which is used as a film-forming polymer.

In the above method for producing the monomer, examples of the (meth)acrylic acid halide used include acrylic acid chloride, methacrylic acid chloride, acrylic acid bromide, and methacrylic acid bromide, and examples of the metal salt of Mana Lewis acid include hexafluoride. Silver antimony, silver tetrafluoroborate, silver perchlorate, etc. are used.

The reaction is carried out according to a conventional method, for example, by dropping a predetermined amount of Te1-Cow Dorofuran into a solution containing a (meth)acrylic acid halide and a Lewis acid metal salt, heating and stirring, and adding water, an aqueous alkali solution, or an aqueous aqueous solution. The reaction is stopped at the desired degree of polymerization of oxyteI/ramethylene by dropwise addition of quaternary ammonium oxide. As alkaline aqueous solutions, sodium hydroxide, potassium hydroxide,
Examples include aqueous solutions of lithium hydroxide, calcium hydroxide, etc. Examples of quaternary ammonium hydroxide include tetramethylammonium hydroxide and tetraethylammonium hydroxide. Furthermore, in the above reaction, a solvent such as dichloromethane which does not affect the reaction may be used if desired.

According to the second method, such a monomer composition is subjected to ring-opening polymerization of tetrahydrofuran with strong pro-1-henic acid, and the polymerization reaction is stopped with a metal salt of (meth)acrylate or an amine salt of (meth)acrylate. It can be manufactured by a method. Examples of the strong propionic acid include trifluoromethanesulfonic acid, trichloride methanesulfonic acid,
Perchloric acid, hydrofluoric acid, sulfuric acid, chlorinated sulfonic acid, fluorinated sulfonic acid, etc. are used. It is also possible to use a combination of the strong protic acid described in item 1 above and a Lewis acid such as antimony pentafluoride. In addition, (meth)acrylic acid metal salts include sodium salts, potassium salts, lithium salts, magnesium salts, calcium salts, barium salts, and sulfontium salts of acrylic acid or methacrylic acid, and (meth)acrylic acid amines. Examples of the salt include (meth)acrylic acid ammonium salt.

The reaction is carried out in a conventional manner according to the first method.

Since the monomer composition thus obtained uses a ring-opening polymerization method using tetrahydrofuran, it is obtained not as a single compound but as a mixture of substances with somewhat different numbers of repeating units in the oxytetramethylene chain. It is not very meaningful to separate and purify them when used as a polymer, and it is also not preferable for the purpose of protecting the polymerizable vinyl group, so it is sufficient to take the number n of repeating units of the oxytetramethylene chain as an average value. It is.

In addition, if the number of repeating units n is 3 or more, the desired purpose of flexibility can be achieved and it can be taken to a fairly large number, but as n increases, the state changes from liquid to solid. In addition, it is difficult to dissolve in solvents, so in practice it is about 10
0, preferably within the range of 3 to 50.

The acrylic resin used in the present invention is a monomer (as a composition) represented by the formula -J- (wherein R is hydrogen or a methyl group; n is a real number of 3 to 5o). 100 mol%
and 80 mol% of other α,β-ethylenically unsaturated monomers. Polymerization is carried out by any method such as emulsion polymerization, solution polymerization, NAD method, etc.
Although no special means are required, for the purpose of the present invention to obtain a solvent-based coating composition, solution polymerization using an organic liquid diluent carrying a film-forming polymer or an organic liquid compatible therewith can be used. It is convenient to use the NADf method. For coating purposes, the number average molecular weight of the acrylic polymer is preferably within the range of about 1,000 to 10,000. The acrylic resin composition thus obtained has an oxytetramethylene chain with a flexible structure represented by the formula in the resin skeleton,
Since it has a reactive hydroxyl group at the end of its side chain, the resin itself is given extremely desirable flexibility and is highly cross-linkable. Furthermore, when n is about 3-50, it is suitable for paints. It has the characteristics of providing highly desirable low viscosity, yet highly elastic coatings.

In the present invention, in addition to the use of the film-forming polymer described in -, as crosslinked resin particles
The molecule has the formula -R-Y (wherein R is a C1-C6 alkylene or phenylene group which may have a substituent, Y is -Coo)I or -3o3H) as shown in the molecule. It is characterized by using crosslinked resin particles obtained by copolymerizing two or more monomers having α, β-ethylenically unsaturated groups in an aqueous or organic medium in the presence of a resin having the groups shown below. That is. Such resin particles are conveniently produced by an emulsion polymerization method or a NAD method in which a resin having a specific amphoteric group is present as an emulsifier or a dispersant, and the resin particles have a form to which the resin having a specific amphoteric group is attached. In the preparation of high-solid paint compositions, this resin exhibits affinity for volatile organic diluents in paint compositions and is therefore useful for stable dispersion of particles within the system. It also has specific effects. Therefore, in order to stably disperse the crosslinked particles in the coating composition,
There is no need to perform any special modification treatment in advance.

In the present invention, in addition to the above-mentioned crosslinking agents, aminoplast resins such as alkyl etherified melamine resins such as butoxymethyl melanine, methoxy methyl melamine, methoxy butoxy mixed etherified methyl melamine, urea resins, etc., or isocyanate stems free or protected are used. The polyisocyanate compound may also be used as an organic liquid diluent, such as an aliphatic hydrocarbon, an aromatic hydrocarbon, an ester, a ketone, an alcohol or a mixture thereof, and optionally para-toluenesulfone as a curing catalyst. Acids, organic acids such as dodecylbenzene and sulfonic acid and their amine salts, or organic metal compounds such as dibutyltin oxide and dibutyl dilaurate are blended. Although the blending amount of each of these components can be changed significantly depending on the desired purpose of use, etc., the weight ratio of the polymer components is usually 50 to 99.5% for the film-forming polymer (A).
part and crosslinked copolymer fine particles (C) 50 to 0.5 parts, and the crosslinking agent (D) is the polymer component (^) + (C) 100 parts.
5 to 100 parts per part, and the organic liquid diluent (B) contains the total amount of polymer component and crosslinking agent (A>+ (C) + (D)
It is blended in a weight ratio of 10 to 2000 parts per 100 parts.

The coating composition of the present invention can be used as a clear coating, but it can also be used as a color base coating by containing metal or non-metallic pigments, and can also be used as a color base coating if desired. Paint additives may also be added.

As already mentioned, since the coating composition of the present invention uses a new resin with low viscosity, high crosslinking reactivity, and high elasticity, the solid content is much larger than the 45-50% volumetric solid content limit using conventional acrylic resins. Not only is this possible, but because cross-linked resin particles are added using a special manufacturing method that does not adversely affect the physical properties of the film, the filler effect of the resin particles can significantly improve sagging properties despite the low viscosity of the film-forming resin. Moreover, due to the characteristics of the film-forming resin, it is possible to provide a coating film with excellent smoothness, toughness, and appearance, and it can be used as a top coat or intermediate coat for automobiles, home appliances, etc. An extremely ideal coating composition can be obtained.

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

(Left space below) The present invention will be described in detail below using Examples ζ, but it goes without saying that the technical scope of the present invention is not limited to these Examples.

(Manufacture of Nanatsumer-a constituting a film-forming polymer) Monomer a represents a compound represented by the following structural formula.

Here, R: Hor Cll3 n: Actual production example 1° of 3 to 50 A well-dried 31 flask has a water content of 1. After sufficient nitrogen substitution with high-purity nitrogen gas of ppm or less, distilled T
13 parts g of HF and 73.8 g of silver antimony hexafluoride were carefully charged so as not to bring in moisture, and the mixture was cooled to -40°C while stirring. Reaching the specified temperature / wheat, T
Add 22.5 g of methacrylic acid chloride to HF+8F and continue the reaction at the same temperature.
After 180 minutes, 450 ml of ion-exchanged water was added to stop the reaction. After the reaction was completed, the reaction solution was taken into a separating funnel, ether was added thereto, ion-exchanged water was added thereto, and the mixture was shaken vigorously. The standing condensate layer was removed. Thereafter, washing with water was repeated several times, and the ether layer was separated.

After dehydration with anhydrous sodium sulfate, the ether was removed under reduced pressure at 20°C using an evaporator, and monomer a-1
I got it.

As a result of measurement by IR and H-NMR, the THF average degree of polymerization n of monomer a-1 was 6.

Production Example 2 In the same manner as in Production Example 1, the reaction was carried out under polymerization conditions of -20°C and 0 minutes to obtain 74 g of monomer a-2.

As a result of measurement by IR and H-NMR, monomer a,
The THF average degree of polymerization n of -2 was 10.

(Production of film-forming polymer) Production Example 3 90 parts of Tsurupez-100 (Note 1) was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas introduction tube, and a dropping row 1, and nitrogen gas 150°C while introducing
After heating for 17 minutes, the following mixture was added dropwise at a constant rate over 3 hours using a dropping funnel.

Mixture A: 160 parts of monomer, 1-40 parts of methyl methacrylate, 5 parts of t-butylperoxy, 2-ethylhexanoate. Drop a mixture of 0.5 parts of Noeito and 10 parts of Norpetzu 100 at a constant speed over 30 minutes.
-Na. After the addition was completed, the mixture was aged at 150°C for 1 hour and then cooled.

The solvent was removed from the obtained solution using an evaporator to obtain a predetermined solid content concentration to obtain a resin solution A-1.

Table 2 shows the properties of the obtained resin and resin solution.

Production Examples 4 to 7 The reaction was carried out in the same reaction vessel and in the same manner as in Example 1 using the composition and reaction temperature shown in Table 1, and after removing the solvent, resin solutions A-2 to A-5 were obtained. Table 2 shows the properties of the obtained resin and resin solution.

(Production of polymer fine particles) Production Example 8 (a) Production of polyester resin having an amphoteric group In a 21-kolben equipped with a stirrer, a nitrogen introduction pipe, a temperature control device, a condenser, and a decanter, 134 parts of bishydroxyethyl taurine, 130 parts of neopentyl glycol,
236 parts of azelaic acid, 186 parts of phthalic anhydride, and 27 parts of quijirole are charged, and the temperature is raised. Water produced by the reaction is removed by azeotroping with quijirole. The temperature was raised to 190°C over about 2 hours from the start of reflux, and stirring and dehydration were continued until the acid value equivalent to carboxylic acid reached 145.
Cool to °C. Then, while maintaining the temperature at 140°C, 3 parts and 4 parts of Cardura E10 (Persatic acid glycidyl ester manufactured by Shell) were added dropwise over 30 minutes, and then at 2 o'clock.
Stirring was continued for 7 days to complete the reaction. The resulting poly
and ester resin have an acid value of 59, a hydroxyl value of 90,
The number average molecular weight was 1054.
1(b) Production of polymer fine particles Into 11 reaction vessels equipped with a stirrer, a cooling tube, and a temperature control device, 282 parts of deionized water, 10 parts of the above polyester resin (a>), and 0.0 parts of dimethylethanolamine were added. 75
4.5 parts of azobiscyanovaleric acid and 4.4 parts of deionized water were added to the mixture and dissolved while stirring while maintaining the temperature at 80°C.
A solution of 5 parts and 4.3 parts of dimethylethanolamine is added. Then methyl methacrylate 7o, 7 parts,
94.2 parts of n-butyl acrylate, 70.7 parts of styrene
A mixed solution of 30 parts of 2-hydroxyethyl acrylate and 4.5 parts of ethylene glycol dimethacrylate was added dropwise over a period of 60 minutes. After the addition, 1.5 parts of azobiscyanovaleric acid dissolved in 15 parts of deionized water and 1.4 parts of dimethylethanolamine was added.
When stirring was continued for 60 minutes at 0°C, non-volatile content was removed! 5%
,pb? , 2, viscosity 92 cps (25°C), particle G,
A 156 μm emulsion is obtained. This emulsion was spray-dried to obtain zero-polymer fine particles B-1.

Coagulation Example 9 (a> Production of modified epoxy resin having amphoteric group) Using the same equipment as in Production Example 8, 73.5 parts of taurine sulium salt, 100 parts of ethylene glycol, and ethitone glycol monomethyl ether were added. Add 200 parts and heat while stirring to raise the temperature to 120°C. After the contents reach a uniform state of dissolution, add Epicote 1001 (
A solution consisting of 470 parts of bisphenol A dicrycidether type epoxy resin manufactured by Shell Co., Ltd. (epoxy equivalent: 470) and 400 parts of ethylene glycol was added dropwise over 2 hours. After dropping, the reaction was completed by continuing stirring and heating for 20 hours. The reaction product was purified and dried to obtain 518 parts of a modified epoxy resin. The acid value of this resin was 49.4. .

(I) Production of polymer fine particles Add 200 parts of deionized water and 0.2 parts of 1-ethylamine to a stainless steel container, stir with a disper, then add 5 parts of the modified epoxy resin obtained in (a) above. The temperature of the mixture was raised to 70°C and stirred for 10 minutes, resulting in a slightly cloudy aqueous solution.Then, this aqueous solution was charged into a reaction vessel similar to that used in Production Example 8, and deionized. Add 106 parts of water and raise the temperature to 80°C while stirring.
was held at To this, 4.5 parts of azobiscyanovaleric acid, I
・Add a mixed aqueous solution consisting of 1.9 parts of ethylamine and 45 parts of deionized water, and while maintaining the temperature at 80°C, add 150 parts of methyl methacrylate, 142 parts of n-butyl acrylate, and 1.8 parts of glycidyl methacrylate. A mixed solution consisting of 1.2 parts of methacrylic acid was added dropwise over a period of 120 minutes. After dropping, add azobiscyanovaleric acid 1 at the same temperature.
35 parts of triethylamine, and 15 parts of deionized water was added and stirring was continued for 60 minutes to obtain a solution with a non-volatile content of 45%, a pH of 7.2, and a viscosity of 69e.
ps (25°C), obtain an emulsion with a particle size of 0.172 Jl. This emulsion was spray-dried to obtain polymer fine particles B-2.

Example 1 Materials having the following composition were weighed into a stainless steel container and stirred using a laboratory stirrer to prepare a coating composition.

-Spicy 1 ,,,,,,,,,,,n-
1--Fire's Dan (f'-↓-ratio's bite 1-)---Polymer fine particles B-11 Resin solution A-19494 Zymel 303 (Note 1) 36 36 Rutile type titanium oxide 81 811 Luol
]2 12n-butanol
1.2 12 Moda Flow (Note 2)
0.2 0.2 Balatoluene sulpone 2.4 2.4 acid l-ethylamine salt This is butyl acetate/kijirole/turpetz-10
When diluted using a mixed solvent of 0 (Note 3) = 2/2/1 with a #-1 food cup at a viscosity of 23 seconds (20°C), the volumetric solid content of the composition of this example] was 61%. The volumetric solid content of Comparative Example was 60%. 1: The film thickness of Example 1 had a sag limit of 48 μm when sprayed, and that of Comparative Example 1 had a film thickness of 34 μm.

Confirmed Example 2 A coating composition having the following composition was prepared using the same method as in Example 1.

−” [−−−−−−−−1−−−−Serial−−− Implementation−Example 4− Ratio J! [2,,,,, -Polymer fine particles B-11 Resin solution A-29494 Cymel 303 36 36 Rutile type titane oxide 81 8] Doluol
1-2 12n-butanol
12 12Modaf o -0,20,2 Para-toluenesulfone 2.4 2.4 acid triethylamine salt This was mixed in a #4 Ford cup using a mixed solvent of butyl acetate/quidylol, ・'Turupetzu 100 = 2/2/1 When diluted to a viscosity of 23 seconds (20°C), Example 2
The volumetric solids content of the composition was 5995, and the volumetric solids content of Comparative Example 2 was 58%.

Further, the film thickness of Example 2 had a sag limit of 49μ when sprayed, and that of Comparative Example 2 had a thickness of 35μ.

Example 3 A coating composition having the following composition was prepared using the same method as in Example 1.

E1 Eclipse 1 Lllll Polymer fine particles B-11 Resin solution A-39494 Cymel 303 36 36 Rutile type titanium oxide 81 81 Doluol
12 12n-butanol 12
12 moda flow 0.2
0.2 para-toluene sulfone 2.4
2.4-acid triethylamine salt This is butyl acetate/Kijirol/Tsurpetz-10
When diluted with a #4 Ford cup to a viscosity of 23 seconds (20°C) using a mixed solvent of 0 = 2/2/1, the volume solids content of the composition of Example 3 was 60%, and that of Comparative Example 3. The solids content by volume was 59%.

Further, the film thickness of Example 3 had a sag limit of 47μ when sprayed, and that of Comparative Example 3 had a thickness of 33μ.

Example 4 A coating composition having the following composition was prepared using the same method as in Example 1.

E1” Support L1 Takumi Support Polymer Fine Particles B-12 Resin Solution A-4107107 Cymel 30B 24 24 Alpeist 1109MA 18 18 (Note 4) Drol 12 12n-Butanol 66 Butyl Acetate 66 Modaflow 0.2 0.2
Paratoluenesulfone 2.4 2.
4-acid triethylamine salt This is ethyl acetate/dolol/Tsurpetz-10
When diluted with a #4 Ford cup to a viscosity of 23 seconds (20°C) using a mixed solvent of 0 = 315/2, the volume solids content of the composition of Example 4 was 60%, and the volume of Comparative Example 4 was Solid content was 59%.

Further, the film thickness of Example 4 had a sag limit of 45μ when sprayed, and that of Comparative Example 4 had a thickness of 34μ.

In addition, the material of Example 4 had good metal retention.

Example 5 A coating composition having the following composition was prepared using the same method as in Example 1.

Round 115LIL Randomi Polymer Fine Particles B-12 Resin Solution A-59494 Cymel 303 36 36n-Butanol 66 Solbetsuso 100 24 24Modaflow 0.2 0.2 Para-Toluenesulfone 2.4 2.4 Acid Triethylamine Salt 100/Tsurupets-150 (
Note 5) When diluted with a #4 Ford cup to a viscosity of 27 seconds (20°C) using a 2/1 mixed solvent, the volumetric solids content of the composition of Example 5 was 62%, compared to the comparative example. The volumetric solids content of No. 5 was 61%.

Further, the film thickness of Example 5 had a sag limit of 50μ when sprayed, and that of Comparative Example 5 had a thickness of 38μ.

Example 6 A coating composition having the following composition was prepared using the same method as in Example 1.

” - 1111 or 11 actual] L example J comparison”
1 Hair-polymer fine particles B-22 Resin solution A71 94 94 Cymel 303 36 36 Rutile type titanium oxide 81 81 Doluol
]2 12n-butanol 1
2 12Modaflow 0.2
0.2 para-toluene sulfone 2.
4 2.4 acid triethylamine salt This is butyl acetate/Kijirol/Tsurpetz-10
When diluted in a #4 Ford cup with a 0=2/2/1 mixed solvent to a viscosity of 23 seconds (20°C), the volumetric solids content of the composition of Example 6 was 61%, compared to that of the comparative example. The volumetric solids content of 6 was 60%.

Further, the sagging limit film thickness of the coating of Example 6 during spray coating was 48 noi, and that of Comparative Example 6 was 34 noi.

Example 7 A coating composition having the following composition was prepared using the same method as in Example 1.

Set 1-1---Seiichi-1--Real J1 example D-U ratio 4 hair example-Dual coalesced fine particles B-11 Resin solution A-19494 Sumidur N-32002020 (Note 6) Rutile type oxidation Titanium 78 78 Doluol 12 ]butyl diacetate
12 12 moda flow
0.2 0.2 This material is converted into butyl acetate/
Viscosity 23 seconds (20 °C
), the volume solids content of the composition of Example 7 was 6
2%, and the volumetric solid content of Comparative Example 7 was 61%.

In addition, the film thickness of Example 7 had a sag limit of 48 μm when sprayed, and that of Comparative Example 7 had a thickness of 34 μm.

Note 1 Methylated melamine manufactured by Mitsui Toatsu Chemical Note 2
Belling agent Note 3, Note 5 manufactured by Monsando Aromatic solvent Note 4 manufactured by Esso Standard Aluminum pigment Note 6 manufactured by Toyo Aluminum Billet type polyisocyanate manufactured by Sumitomo Bayer

Claims (5)

[Claims] (1) A film-forming polymer (A) having a functional group capable of reacting with a crosslinking agent, a volatile organic liquid diluent (B) supporting the polymer, and insoluble in the combination of the polymer and diluent. It consists of fine polymer particles (C) stably dispersed in the diluent, and a crosslinking agent (D) dissolved in the diluent, and the fine polymer particles (C) have a formula -■- in the molecule. RY (wherein, R is C_1 to C_6 which may have a substituent)
monomer having two or more α,β-ethylenically unsaturated groups in an aqueous or organic medium in the presence of a resin having a group represented by an alkylene or phenylene group, Y is -COOH or -SO_3H) The film-forming polymer (A) is a cross-linked copolymer fine particle obtained by copolymerizing the following: Number average molecular weight 1000-100 with side chains
A coating composition characterized in that it is an acrylic polymer or copolymer of No. 00. (2) The weight ratio of the polymer components to the film-forming polymer (
A) 50 to 99.5 parts and crosslinked copolymer fine particles (C) 50 parts
~0.5 part, and the crosslinking agent (D) is the polymer component (A)
5 to 100 parts per 100 parts of +(C), and the organic liquid diluent (B) contains the total amount of polymer component and crosslinking agent (A) + (
2. A composition according to claim 1, in a proportion by weight of 10 to 2000 per 100 parts of C)+(D). (3) The composition of claim 1, wherein the volatile organic liquid diluent is an aliphatic hydrocarbon, an aromatic hydrocarbon, an ester, a ketone, an alcohol, or a mixture thereof. (4) The composition according to claim 1, wherein the crosslinking agent is an aminoplast resin or a polyvalent isocyanate compound whose isocyanate stems may be free or protected. (5) The composition according to claim 1, which contains a metal or non-metal content.