JPS6218479A - Water-dilutable matte coating composition - Google Patents

Abstract

PURPOSE:To provide the titled coating compsn. exhibiting an improvement in the resistance to change with time, matte effect and resistance to chemicals of coating film, by blending a specified fine dispersion of a polymer neutralized with an alkali, an acrylic copolymer and an aminoplast resin. CONSTITUTION:The coating compsn. is a mixt. of (I) fine dispersion of a polymer obtained by copolymerization of a monomer mixt. consisting of a glycidyl group-contg. monomer and a carboxyl group-contg. monomer in a soln. of a carboxyl group-contg. polymer for crosslinking reaction of at least part of the glycidyl and carboxyl groups, (II) acrylic copolymer contg. carboxyl and alkoxyalkyl groups linked to the hydroxyl group and/or N and (III) aminoplast resin, with at least part of (I) and (II) being neutralized with am alkali to make the compsn. dilutable with water.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a water-dilutable matte coating composition that is used for building materials, housings of various equipment, etc. [Background of the Invention] Aluminum sash, It is desirable to paint building materials such as panels, fences, gates 8, electronic equipment 2 analysis equipment, housings of office equipment, etc. with matte paints, and for this purpose, matte paints that can be mass-produced are recommended, especially for work environments, hazards, etc. From this point of view, it is desired to provide a water-dilutable matte paint.

[Conventional technology]

Conventionally, the following techniques have been provided for producing this type of water-dilutable matte paint.

Prior art 1: A method of blending and dispersing fine inorganic powders such as silica-based and aluminum-based powders, and organic fine powders such as polyethylene and fluororesin into paint.

Prior art 2: A method of blending and dispersing crosslinked synthetic resin fine powder in a paint. The crosslinked synthetic resin fine powder can be produced by, for example, a method of polymerizing a polyvalent vinyl compound such as trimethylolpropane triacrylate or methacrylate or trimethylolmethane triacrylate or methacrylate in a synthetic resin solution (Japanese Patent Publication No. 59-34743, Japanese Patent Publication No. 59-37027), a method of reacting an epoxy compound with a carboxyl group-containing aqueous resin (Japanese Patent Publication No. 59-37027),
138278), a method of reacting alkoxylated methylol melamine and αβ-ethylenically unsaturated polycarboxylic acid resin in an aqueous emulsion state (JP-A-58-8486)
No. 9, JP-A-58-215466, JP-A-59-33
No. 368), Method for obtaining internally crosslinked emulsion copolymers by copolymerization of polyfunctional vinyl monomers and monofunctional vinyl monomers (Japanese Unexamined Patent Publication No. 58-93762), Water-based acrylic resin and alkoxysilane (Japanese Patent Application Laid-Open No. 59-67396), a method of copolymerizing a multifunctional crosslinking monomer with other vinyl monomers to obtain a multilayered polymer latex (Japanese Patent Application Laid-Open No. 59-74171) etc. are provided.

Conventional technology 3: [As a matte coating method for electrocoating, the uncured coating film after electrodeposition is immersed in an acidic aqueous solution (
JP-A-52-137444 - JP-A-52-13744
No. 7), or a method of immersing the uncured coating film in an acidic aqueous solution or its salt and treating it with electricity (Japanese Patent Publication No. 59-3367
No. 5, Japanese Unexamined Patent Publication No. 59-229494).

[Problem that the invention seeks to solve]

When using inorganic fine powder in Prior Art 1, the fine powder settles or floats in the paint, resulting in poor dispersion stability, and since the inorganic fine powder is hard, it easily falls off from the paint film, resulting in a durable matte state. There is a problem that it is not possible to obtain
When organic fine powder is used, there are problems in that the dispersion stability is insufficient, the matting effect disappears due to softening due to heat, and the solvent resistance is poor.

In conventional technology 2, a means called crosslinking is used to impart heat resistance and solvent resistance to the organic fine powder used in conventional technology 1, but there is a problem with the dispersion stability of the fine powder, and the matting effect changes over time. In addition, the matting effect is not sufficient and complete matting (gloss value 10 or less) is not possible, or the coating conditions (for example, in the case of electrodeposition coating, bath IA, pH, amount of solvent contained, distance between electrodes, etc.) There was a problem in that the gloss value fluctuated too much due to fluctuations in solid content (solid content, etc.) and film thickness.

In Conventional Technology 3, since fine powder is not dispersed as a matting agent, there is no problem with dispersion stability, but there are problems with aging of the processing liquid, and the matting effect is still not sufficient.
There were various problems such as a decrease in the chemical resistance of the coating film.

[Means for solving problems]

As a means to solve the above conventional problems, the present invention copolymerizes a monomer mixture containing a glycidyl group-containing monomer and a carboxyl group-containing monomer in a carboxyl group-containing polymer solution, and A fine particulate polymer dispersion (I) obtained by crosslinking at least a portion of the glycidyl group of the containing monomer and the carboxyl group of the carboxyl group-containing monomer, the carboxyl group, the hydroxyl group and/or Alternatively, in a mixture of an acrylic copolymer (II) containing an alkoxyalkyl group bonded to a nitrogen atom and an amino 7° last resin (■), a fine particulate polymer dispersion (I) and an acrylic copolymer Union (I)
provides a water-dilutable matte coating composition which is made water-dilutable by being at least partially neutralized with an alkali.

The present invention will be explained in detail below.

Particulate polymer dispersion (I) The carboxyl group-containing polymer used for producing the dispersion (I) is acrylic acid, methacrylic acid, maleic acid, maleic acid monoester, itaconic acid, itaconic acid monoester, crotonic acid. , c) one or more vinyl polymerizable α-β unsaturated fatty acids such as 7conic acid, and methyl acrylate or methacrylate, ethyl acrylate or methacrylate, isopropyl acrylate or hamethacrylate, normal butyl acrylate or methacrylate, 2 - ethylhexyl acrylate or methacrylate, cyclohexyl acrylate or methacrylate, lauryl acrylate or methacrylate, styrene, alpha-methylstyrene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride,
Acrylonitrile, methacrylate trile, vinyl fluoride,
Vinylidene fluoride, β-hydroxyethyl acrylate or methacrylate, β-hydroxyglobil acrylate or methacrylate, acrylamide, N-
Methyloracrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxymethylacrylamide, methacrylamide, N-
Methylol methacrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl methacrylamide,
A copolymer of one or more monomers copolymerizable with the above α-β unsaturated fatty acids such as N-butoxymethylacrylamide, dimethylaminoethyl acrylate or methacrylate, dimethylaminoinglobil acrylate or methacrylate. The content of carboxyl groups in the copolymer may be sufficient as long as the copolymer can acquire water dilutability through alkali neutralization, and usually has an acid value of about 30 to 100. preferable. Furthermore, it goes without saying that the carboxyl group-containing polymer includes all carboxyl group-containing alkyd resins, carboxyl group-containing polyesters, carboxyl group-containing petroleum resin rings, and generally synthetic resins containing carboxyl groups.

The carboxyl group-containing polymer is preferably water, or a cellosolve solvent such as methanol, ethanol, Impropano-A4(7) lower aliphatic alcohol, methylcellosolve, ethyl cellosolve, n-butyl cellosolve, ethylene glycol, 10-pyrene glycol, or It is provided as a solution of a polyhydric alcohol such as methylolpropane, glycerin, or a water-miscible solvent such as acetone, and the solid content is usually 10 to 50% by weight. Polymerization is carried out using known methods such as solution polymerization, emulsion polymerization, and suspension polymerization. method was applied, and the molecular weight was 5000 to 1oooo.

That's about it.

A monomer mixture containing a glycidyl group-containing monomer and a carboxyl group-containing monomer is copolymerized in the carboxyl group-containing polymer solution. The above-mentioned glycidyl group-containing monomers include glycidyl acrylate, methacrylate, glycidyl allyl ether, etc., and the dicarboxyl group-containing monomers include acrylic acid, methacrylic acid, maleic acid, maleic acid monoester, itaconic acid, and itaconic acid monoester. , crotonic acid, citraconic acid, etc. The above glycidyl group-containing monomer and carboxyl group-containing monomer are each
or a mixture of two or more thereof, and if desired, methyl acrylate or methacrylate, ethyl acrylate or methacrylate, inglovir acrylate or methacrylate, n-butyl acrylate or methacrylate, 2-ethylhexyl acrylate or methacrylate, cyclohexyl acrylate or methacrylate, lauryl. Acrylate or methacrylate, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride,
Acrylonitrile, methacrylate trile, vinyl fluoride,
One or more types of other monomers copolymerizable with the above glycidyl group-containing monomer and carboxyl group-containing monomer, such as vinylidene fluoride, may be mixed. However, it is desirable that the total amount of the glycidyl group-containing monomer and the carboxyl group-containing monomer be 50 m or more in the monomer mixture. The mixing ratio of the above-mentioned glycidyl group-containing monomer and carboxyl group-containing monomer is preferably such that the glycidyl group/carboxyl group is in an equivalent ratio of 0.8 to 1.2, but the most desirable one is a 1 equivalent ratio. It is.

The monomer mixture is polymerized in the carboxyl group-containing polymer solution. The polymerization method is a method of heating the carboxyl group-containing polymer solution and sequentially adding the monomer mixture and a polymerization initiator to the solution (Japanese Patent Application Laid-Open No. 5-11101).
No. 8-40310) is recommended, but other known polymerization methods may be applied. The above-mentioned monomer mixture is added to the above-mentioned carboxyl group-containing polymer solution in a wide range of amount from 10 to 300 i. It seems that the degree of involvement is hereditary. The above monomer mixture is polymerized in the above carboxyl group-containing polymer solution as described above, but a crosslinking reaction between carboxyl groups and glycidyl groups occurs in parallel with the progress of polymerization, and the polymer is formed. It is observed that the reaction system becomes cloudy due to insolubilization in the solution. Although the crosslinking reaction occurs naturally under the polymerization conditions described above, a reaction catalyst such as triethylamine, diisoglobilamine, triethanolamine, etc. may be added to further promote the crosslinking reaction. Furthermore, in order to adjust the viscosity of the reaction system, a solvent similar to the solvent used for the carboxyl group-containing polymer solution may be added during the polymerization. In this way, a dispersion (I
) is obtained. The above dispersion (I) may be used as it is, or if desired, the above particulate polymer may be further refined by a sand mill, a ball mill, etc. Acrylic copolymer (I) Acrylic used in the present invention The copolymer (...) contains a carboxyl group, a hydroxyl group, and/or an alkoxyalkyl group bonded to a nitrogen atom. In order to introduce a carboxyl group into the above acrylic copolymer (I1), vinyl polymerizable materials such as acrylic acid, methacrylic acid, maleic acid, maleic acid monoester, itaconic acid, itaconic acid monoester, crotonic acid, citraconic acid, etc. By copolymerizing IF5 or two or more types of α-β unsaturated fatty acids. To introduce a hydroxyl group and/or an alkoxyalkyl group bonded to a nitrogen atom into the acrylic copolymer (I), β-hydroxyethyl acrylate or methacrylate, β-hydroxyglobyl acrylate or methacrylate, N-methylol acrylamide, N - One or more hydroxyl group-containing monomers such as methylol methacrylamide and allyl alcohol, and the hydroxyalkyl group in the hydroxyalkyl group-containing monomer bonded to the nitrogen atom, such as methanol, ethanol,
By copolymerizing one or more alkoxyalkyl group-containing monomers modified with alcohols such as Impropatol, normal butanol, and inbutanol. The alcohol modification may be performed after copolymerizing the hydroxyl group-containing monomer. The above acrylic copolymer (f
i) further includes acrylic components such as methyl acrylate or methacrylate, ethyl acrylate or methacrylate, inglovir acrylate or methacrylate, normal butyl acrylate or methacrylate, 2-ethylhexyl acrylate or methacrylate, cyclohexyl acrylate or methacrylate, lauryl acrylate or methacrylate, etc. One or more types of acrylic ester and/or methacrylic ester are copolymerized, but in addition to the acrylic ester and/or methacrylic ester, the above α
- styrene, which is another monomer copolymerizable with β-unsaturated fatty acids, hydroxyl group-containing monomers, and alkoxyl group-containing monomers;
α~Methylstyrene, vinyl acetate, vinyl propionate, vinyl chloride, vinylitine chloride, acrylonitrile, methacrylaterile, vinylidene fluoride, vinylidene fluoride, etc. may be copolymerized.

In the above acrylic copolymer (I), the carboxyl group may be contained in an amount sufficient for the copolymer (I) to acquire water dilutability, usually in an acid value of about 30 to 100. Desirably, a monomer containing a hydroxyl group and/or an alkoxyl group is incorporated into the acrylic copolymer (I) in an amount of usually 1 to 30% by weight. The above acrylic copolymer (I) can be polymerized by known methods such as solution polymerization, emulshore polymerization, suspension polymerization, etc., but methanol, ethanol, isopropanol, methyl cellosolve, ethyl cellosolve, n-butyl cellosolve, Solution polymerization using water-miscible solvents such as ethylene glycol, 10-pyrene glycol, trimethylolpropane, glycerin, etc. is preferred.

Aminoblast resin (I) Aminoblast resin used in the present invention Melamine,
A condensate of an amine compound such as urea or benzoguanamine and an aldehyde compound such as formaldehyde or acetaldehyde, or a modified condensate obtained by further denaturing the condensate with an alcohol such as methanol, ethanol, ingropanol, or normal butanol. It is desirable to have dilutability, and usually methanol, ethanol,
Ingbanol, methyl cellosolve, ethyl seronulf, n-butyl cellosolve, etele/cricol,
It is provided as a solution using a water-miscible solvent such as propylene glycol, trimethylolpropane, or glycerin, and the total solid content of the coating composition of the present invention is usually 5 to 5.
0 weight: approximately ft% is added.

Neutralization In the mixture of the fine particulate polymer dispersion (I), the acrylic copolymer (I), and the aminoblast resin (I), the fine particulate polymer dispersion (I) and the acrylic copolymer Coalescence (I) is at least partially neutralized by alkali. Examples of alkalis used include ammonia, trimethylamine, triethylamine, triethanolamine,
Inorganic alkalis such as dimethylethanolamine, diethylethanolamine, triisoglopanolamine, dimethylimpropanolamine, dietheringlobanolamine, etc., and organic amines are used, but in the present invention, volatile alkalis can be used. In particular, from the viewpoint of paint stability and neutralizing power, tertiary amines and alkanolamines such as those exemplified above are preferable. The fine particulate polymer dispersion (I) and the acrylic copolymer (
Neutralization with I) may be carried out individually prior to preparing the above mixture, or may be carried out on a mixture of the particulate polymer dispersion (I) and the acrylic copolymer (I). It may also be carried out on the final mixture.

In this way, the mixture acquires water dilutability by being at least partially neutralized by the alkali.

[Effect]

The effects of the present invention based on the above configuration are as follows.

The particulate polymer contained in the coating composition of the present invention is present in the coating film, and by forming minute irregularities on the coating film surface, light is diffusely reflected and a matting effect is exerted. The particulate polymer is an organic substance and has good affinity with the diacrylic copolymer, and because of crosslinking, it is not easily softened by heat and exhibits solvent resistance. The carboxyl group-containing polymer acquires water dilutability through alkali neutralization and at the same time stably disperses the fine particle polymer. When the total amount of the glycinol group-containing monomer and the carboxyl group-containing monomer in the fine particle polymer is 50% by weight or more, the production rate of the fine particle polymer is improved, the dispersion stability is further improved, and the heat resistance is improved. , solvent resistance is also improved. Furthermore, the dispersion stability of the coating composition of the present invention is also affected by the good affinity of the fine particle polymer with the acrylic polymer and the fact that the carboxyl groups remaining in the fine particle polymer are neutralized with alkali. It is assumed that the The aminogellast resin (I) reacts with the acrylic copolymer (I) under heating to form a crosslinked structure, thereby providing a coating film having heat resistance, solvent resistance, and high mechanical strength.

〔Effect of the invention〕

Therefore, in the present invention, the dispersion stability of the fine particle polymer is extremely good, and the matte state of the coating film is durable.
It has excellent solvent resistance and heat resistance, and the coating film itself has good solvent resistance and heat resistance, as well as excellent mechanical strength.

The matte coating composition of the present invention is capable of providing various gloss values from completely matte to semi-matte, has small changes in gloss even when the thickness of the coating film varies, and is also suitable for electrodeposition coating. Even when applied to a large-scale painting process on a line, there is little variation in gloss due to changes in painting or external conditions or factors, and the paint remains stable for a long time, making it suitable for aluminum construction materials such as aluminum sashes and panels. It is useful for industrial coating methods that are required in a wide range of fields such as paint and various types of equipment. .

〔Example〕

The present invention will be specifically explained below using examples. All composition ratios on each side below are based on weight, and substance names are indicated using the symbols below.
: Inbutyl acrylate HA: 2-ethylhexyl acrylate HEA: Hydroxyethyl acrylate HEMA: Hydroxyethyl methacrylate AA: Acrylic acid MAA: Methacrylic acid N-MAM: N-methylolacrylamide TFJ
A: Triethylamine DMEA: Dimethylethanolamine ABN
: Azobisisobutyronitrile HPA : Hydroxyethyl acrylate MMA : Methyl methacrylate St : Styrene [Preparation of carboxyl group-containing polymer solution and acrylic copolymer (I) solution] In a 31 flask equipped with a stirrer, condenser, and thermometer. 50 parts of butyl cellosolve and 61 parts of inpropanol were charged and heated to 80°C.
500 copies, MMA 400 copies.

A mixed monomer solution of 20 parts of ABN dissolved in 100 parts of MAA mixed monomer was continuously added dropwise for 6 hours, and then heated at the same temperature for another 2 hours to form a carboxyl group-containing polymer solution A with a solid content of 60 parts. Obtained. Polymer solutions B-F having the compositions shown in Table 1 were obtained in exactly the same manner.

In the following examples, the above polymer solutions B-F are acrylic copolymers (I) as carboxyl group-containing polymers.
Also used as

Table 1 [Example 1] 334 g of carboxyl group-containing polymer solution A, 200 parts of butyl cellosolve, and 466 parts of inpropanol were charged into a No. 31 flask equipped with a stirrer, a condenser, and a thermometer, and the temperature was raised to 80°C. Then 100 copies of GiVIA, A
A mixed monomer solution of 4 parts of ABN was added to a monomer mixture of 60 parts of A and 40 parts of MMA, and then d part of ABN and 600 parts of impropanol were added to the monomer mixture of 100 parts of GMA, 60 parts of AA, and 40 parts of MMA. The mixture was added dropwise continuously for 3 hours. After that, the mixture was stirred while maintaining the temperature at 80°C for 4 hours.
During this time, the reaction was terminated by adding 4 parts of ABN three times every 60 minutes.

The resulting fine particulate polymer dispersion (I) was further micronized using a batch type sand mill for 60 minutes to obtain a dispersion having a solid content of 30 cm.

600 parts of the present fine particle polymer dispersion (I), 167 parts of acrylic polymer (I) solution F', melamine resin manufactured by Sanwa Chemical Co., Ltd. (trade name Nikaratsuku MW-40) as aminoblast resin (III) ) 120 parts, TEA1
After neutralization in parts, 95 parts of water was added to obtain a matte paint with a solid content of 40 g.

Dilute 500 parts of this matte paint with 1500 parts of water, solid content 1
A 0% electrocoating paint was prepared, the pH was further adjusted to 7 or 8 using TEA, and a bath was prepared in 21 electrodeposition baths. Secondary electrolytic method Bronze color anodized aluminum (film thickness 9μ, 8X153) is used as an anode, distance between electrodes is 15, bath temperature is 25℃, 120V/
Electrodeposition coating by applying electricity for 3 minutes and 190℃ after washing with water.
Baked and dried for 30 minutes.

The resulting film had a thickness of 9 μm and a gloss (60° reflectance) of 22.
A uniform matte coating surface with good smoothness was obtained.

This electrodeposition bath was sealed and left at 50°C for one week. Although some sediment was observed, it was easily redispersed by stirring, and when electrodeposition was applied under the same conditions as above, the film thickness was A good matte coating with a gloss of 9.5μ and a gloss of 20 was obtained.

[Examples 2 to 5] By the same operation as in Examples, 134 parts of GMA, 66 parts of AA, and part ABNJ were added at 80°C in a solution in which 526 parts of impropanol was added to 616 parts of carboxyl-containing polymer solution C. Addition, followed by 134 parts of GMA, 66 parts of AA, A
A mixed solution of 4 parts of BN and 466 parts of IPA was continuously added for 2 hours. After the addition was complete, 3 parts of TEA was added, and the reaction was then continued for an additional 4 hours, during which time 3 parts of ABNa was added every hour.
Added twice. The obtained dispersion was processed in a batch type sand mill for 6
Pulverized for 0 minutes to obtain a fine particulate polymer dispersion with a solid content of 40% (
I) was obtained. Using this dispersion (I), the formulations shown in Table 2 were carried out to prepare matte coatings of Examples 2 to 5.

Table 2 This matte paint was diluted with water, and an electrodeposition paint having a solid content of 10% and a pH of 7.8 was prepared in a 21°C deposition bath.

As in Example 1, bronze-colored anodized aluminum (film thickness 9
μ) was electrodeposited. The results are shown in Table 3. By adjusting the amount of fine particle dispersion, a matte coating ranging from completely matte to semi-glossy was obtained. S H8602
All had performance that passed the "composite film of anodic oxidation coating of aluminum and aluminum alloy".

When the electrocoating bath shown in Table 3 was allowed to stand still in a hermetically sealed manner at 50° C. for one week, some sediment was observed, but it was easily redispersed by stirring. When the redispersion was treated with an anion exchange resin and then electrodeposited under the same conditions, the film thickness decreased by about 1 to 2 microns, but the change in gloss increased by 5 in Example 2 and decreased by 2 in Example 3. In Example 4, the gloss decreased by 1, and in Example 5, it increased by 0.1, indicating that the change in gloss was small and stable.

[Example 6] By the same operation as in Example 1, 616 parts of dicarboxyl group-containing polymer solution C was added with 526 parts of inbanol, and 60 parts of GMA1 and 80 parts of AA were added in a mixed monomer solution. A mixed monomer solution dissolved in 4 parts of ABN was heated to 80°C.
, then 2 parts TEA, and after 10 minutes GMA
60 parts of I, 80 parts of AA, 4 parts of ABN, 4 parts of Impropanol, 6 parts.

A mixture of 2 parts TEA was added continuously for 3 hours.

Subsequently, ABNa portion was added twice every hour, and the reaction was continued for 3 hours. The obtained dispersion was milled in a batch type sand mill at 90°C.
A finely divided polymer dispersion with a solid content of 40% (I
) was obtained.

This fine particulate polymer dispersion (I) 440 parts 1 Polymer (I
) 1197 parts of solution C, 98 parts of aminoblast resin (Ill) two-carat (NW-40), 5.5 parts of DMEAI,
A matte paint with a solid content of 40% was prepared by blending 249.5 parts of water.

As shown in Table 4, this matte paint has solid content and pH.

Electrodeposition coating was performed on a bronze colored anodized aluminum plate by changing the electrodeposition conditions such as bath temperature. As a result, the condition of the coated surface was good and there was only a slight change in gloss under various conditions.

[Example 7] A carboxyl group-containing polymer solution was prepared in the same manner as in Example 1. A solution in which 467 parts of butyl cellosolve was added to 666 parts was heated to 90°C, and 124 parts of GMA and 76 parts of MAA were added.
30 minutes later, 24 parts of CMAI, M
A mixture of 76 parts of AA, 4 parts of ABN, and 467 parts of butyl cellosolve was continuously added dropwise for 2 hours. After that, 3 times every 60 minutes
3 parts of BN were added and the reaction was continued for 4 hours.The resulting dispersion was ground in a batch type sand mill for 60 minutes until the solid content was 4.
A finely divided polymer dispersion (I) was obtained.

Main dispersion (I) 400 parts, acrylic copolymer (I)
B, 222 parts, aminogellast resin (■) (Nikaratsuku NW-30 manufactured by Sansho Chemical Co., Ltd.) 97 parts, DMEA 15 parts,
A matte paint with a solid content of 40% was obtained by blending 263 parts of water.

This matte paint was diluted with an IPA/water mixed solvent to a solid content of 30 g, spray painted on a bronze colored anodized aluminum plate, and baked and dried at 180°C for 30 minutes. The resulting coating film had a thickness of 25 μm and a good matte coating surface with a gloss of 78.

In addition, when this paint was applied to a bronze-colored anodized aluminum plate using a percoater and the relationship between film thickness and gloss was investigated, as shown in Table 5, even if the film thickness varied, the change in gloss was slight. .

Table 5 [Example 8] A carboxyl group-containing polymer solution was prepared in the same manner as in Example 1. A solution of 666 parts and 200 parts of butyl cellosolve was heated to 90°C, and 130 parts of GMA, 70 parts of AA, and 1 part of ABNa were added. and then 130 parts of GMA, AA7
A mixture of 0 part ABNa, 200 parts butyl cellosolve was continuously added dropwise over 3 hours. After that ABNZ
The reaction was continued for 3 hours by adding 1 part each twice every 60 minutes to complete the reaction. The obtained dispersion was milled in a batch type sand mill for 60 min.
Fine particulate polymer dispersion (I) with a solid content of 55% after being ground for minutes
I got it.

This particulate polymer dispersion (I) 262 parts, acrylic polymer (M)E, 263 parts, aminoblast resin (■)
100 parts of Karatsuk NW-40), 15 parts of DMEA, and 360 parts of water were blended into the mixture to obtain a matte paint having a solid content of 40 inches.

Disperse 300 parts of this paint and 9.6 parts of carbon black in a paint conditioner for 60 minutes, then dilute with water to prepare a black matte paint with a solid content of 10% and a pH of 8.0.1-
Electrodeposited on silver anodized aluminum plate (film thickness 8μ) and Bonderite #144 treated steel plate at 200°C
As a result of baking and drying for 30 minutes, a good black matte coating was obtained as shown in Table 6. Patent applicant: Toagosei Chemical Industry Co., Ltd. Hand sticky moss 1
J Official Book July 26, 1985 Director General of the Patent Office 1, Indication of Case io-/f-1; ge)
゛- Patent application 2 filed on July 16, 1985, name of the invention Water-dilutable matte paint composition 3, relationship to the case of the person making the amendment Patent applicant address 14 Nishi-Shinbashi-chome, Minato-ku, Tokyo Number 1 Name (30
3) Komori, President and CEO of Toagosei Chemical Industry Co., Ltd.
Takashi 4, Agent 467 Address 32-6 Tsukimigaoka, Yatomi-cho, Mizuho-ku, Nagoya Number of inventions increased by amendment 7 Target of amendment 8 Contents of amendment ■ Page 14, line 9 “/or alkoxyl group” Corrected to "/or an alkoxyl group bonded to a nitrogen atom."

that's all

Claims (1)

[Scope of Claims] Copolymerizing a monomer mixture containing a glycidyl group-containing monomer and a carboxyl group-containing monomer in a carboxyl group-containing polymer solution, and copolymerizing the glycidyl group of the glycidyl group-containing monomer. A particulate polymer dispersion (I) obtained by crosslinking at least a portion of the carboxyl group-containing monomer with the carboxyl group, and an alkoxyalkyl group bonded to the carboxyl group and the hydroxyl group and/or nitrogen atom. In the mixture of the group-containing acrylic copolymer (II) and the aminoblast resin (III), the particulate polymer dispersion (I) and the acrylic copolymer (II) are at least alkali-containing. A water-dilutable matte paint composition characterized by being water-dilutable by being partially neutralized.