JP2005307161A - Anionic electrodeposition coating material and coated artice - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an anionic electrodeposition coating material which is excellent in weatherability, coating stability and die mark screening. <P>SOLUTION: The anionic electrodeposition coating material contains (A) a core/shell emulsion which is an emulsified polymer obtained by emulsion-polymerizing a polymerizable unsaturated monomer by a multi-step reaction in the presence of water and an emulsifier and contains 1-40 wt%, against the total monomer weight used in the multi-step reaction, an alkoxylsilyl group-containing polymerizable unsaturated monomer as the polymerizable unsaturated monomer, (B) an alkyl resin and (C) a hardener. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a matte anionic electrodeposition paint excellent in weather resistance, paint stability, and dice mark concealment, and an article coated with the paint.

Aluminum has been increasingly used as a material especially for building materials, taking advantage of its light weight and easy workability.
The method of hot extrusion of aluminum usually involves heating and melting a cylindrical aluminum ingot, then placing the melt in an extruder and pressing it against a die having a hole with a predetermined cross-sectional shape and passing through the hole. And obtaining a mold material having a predetermined shape.
In general, the aluminum mold itself is inferior in corrosion resistance, abrasion resistance, chemical resistance, etc., and therefore, after the aluminum mold is anodized, the matte coating film is coated with a matte anionic electrodeposition paint. It is common.
However, when the matte anion electrodeposition coating is electrodeposited onto an anodized aluminum mold, there is a problem in that the die mark of the aluminum mold as the material is easily noticeable and the commercial value is inferior.
Conventionally, an emulsion polymer produced by multi-stage emulsion polymerization using a polymerizable unsaturated monomer in the presence of water and an emulsifier, and containing an alkoxysilyl group as the polymerizable unsaturated monomer There is an invention relating to an anionic electrodeposition coating material containing an alkoxysilyl group-containing emulsion polymer containing an unsaturated monomer in a proportion of 5 to 40% by weight based on the total weight of monomers used in multiple stages [Patent Document 1] .
In Patent Document 1, weather resistance and dice mark concealment are insufficient.

In addition, for the purpose of improving the weather resistance, there is an invention relating to an anionic electrodeposition paint comprising an acrylic copolymer resin and an amino resin curing agent containing an ultraviolet absorber and a light stabilizer [Patent Document 2].
]. As in Patent Document 2, the combination of the acrylic copolymer resin with the ultraviolet absorber and the light stabilizer is not sufficiently compatible, and the ultraviolet absorber and the light stabilizer flow out from the coating film over time. Sufficient weather resistance could not be obtained, and there were problems with paint stability over a long period of time.

JP 2002-188044 A

JP 2002-38084 A

  The present invention provides a matte anionic electrodeposition paint excellent in weather resistance, paint stability, and dice mark concealment.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a radical polymerizable unsaturated monomer having an alkoxysilyl group-containing polymerizable unsaturated monomer (a) and an ultraviolet absorber component. At least one radical-polymerizable unsaturated monomer selected from the group (b), a radical-polymerizable unsaturated monomer (c) having a light stabilizer component, and a fluorine-containing radical-polymerizable unsaturated monomer (d) What can be achieved by an anionic electrodeposition coating containing a core / shell type emulsion (A) having a core and a polymer obtained by radical copolymerization of a monomer and other radical polymerizable unsaturated monomer (e) The headline and the invention were completed.

That is, the present invention
“1. An emulsion polymer produced by emulsion polymerization in multiple stages using a polymerizable unsaturated monomer in the presence of water and an emulsifier, and an alkoxysilyl group as the polymerizable unsaturated monomer Core / shell type emulsion (A), acrylic resin (B), curing agent (C) containing a polymerizable unsaturated monomer in a ratio of 1 to 40% by weight based on the total weight of monomers used in multiple stages ) Containing anionic electrodeposition paints,
The core / shell type emulsion (A) is a radical polymerizable unsaturated monomer having an alkoxysilyl group (a) and a radical polymerizable unsaturated monomer having an ultraviolet absorber component in an aqueous solution of water and an emulsifier ( At least one radical polymerizable unsaturated monomer selected from b), a radical polymerizable unsaturated monomer (c) having a light stabilizer component and a fluorine-containing radical polymerizable unsaturated monomer (d) And other radically polymerizable unsaturated monomer (e), and if necessary, a radically polymerizable unsaturated monomer containing monomer (f) containing two or more unsaturated groups in one molecule After producing the radical polymer (I) by performing the first stage radical emulsion polymerization reaction in the presence of a radical polymerization initiator,
Next, in the presence of the above-mentioned radical polymer (I), a radical polymerizable unsaturated monomer (a) having an alkoxysilyl group and other radical polymerizable unsaturated monomers (e), 1 if necessary A core / shell type emulsion obtained by subjecting a radical polymerizable unsaturated monomer containing a monomer (f) containing two or more unsaturated groups in the molecule to a second stage radical emulsion polymerization reaction An anionic electrodeposition paint characterized by
2. The core / shell type emulsion (A) comprises a radical polymerizable unsaturated monomer (b) having an ultraviolet absorber component, a radical polymerizable unsaturated monomer (c) having a light stabilizer component, and fluorine-containing radical polymerization. At least one radically polymerizable unsaturated monomer selected from the polymerizable unsaturated monomers (d) is 0.01% with respect to the total monomer weight constituting the core / shell emulsion (A). The anionic electrodeposition coating material according to item 1, wherein the anionic electrodeposition coating material is contained in a proportion of 10 to 10% by weight.
3. Item 1 or 2, comprising 2- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole as the radical polymerizable unsaturated monomer (b) having an ultraviolet absorber component The anion electrodeposition paint described in item 2.
4). Item 1 or Item 2 comprising 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine as the radically polymerizable unsaturated monomer (c) having a light stabilizer component. Anion electrodeposition paint described in 1.
5). 3. The anionic electrodeposition coating material according to item 1 or 2, which contains 2-perfluorooctylethyl methacrylate as the fluorine-containing radically polymerizable unsaturated monomer (d).
6). A cured coating film obtained by electrodeposition-coating the anionic electrodeposition paint described in any one of items 1 to 5 on an object to be coated has a 60-degree specular gloss as defined in JIS K-8741. Painted article whose is 30 or less. "
About.

The anionic electrodeposition coating material of the present invention can provide a matte coating (60 ° specular gloss specified by JIS K-8741 is 30 or less) excellent in weather resistance, coating stability, and dice mark concealing property. With regard to paint stability, there is no problem in stability even if a mechanical share is applied in the painting line.

Reasons for excellent weather resistance include radical polymerizable unsaturated monomer having an ultraviolet absorber component, radical polymerizable unsaturated monomer having a light stabilizer component, fluorine-containing radical polymerizable unsaturated monomer, etc. Since at least one monomer, which is said to be effective in weather resistance, is incorporated into the polymer of the core part of the core / shell emulsion, these monomer components remain even when the coating film is exposed. It does not flow out of the coating film.

The matte anionic electrodeposition paint excellent in weather resistance and paint stability of the present invention contains a core / shell emulsion (A), an acrylic resin (B), and a curing agent (C). Details are described below.

Core / shell type emulsion (A):
The core / shell type emulsion (A) includes a radical polymerizable unsaturated monomer (a) having an alkoxysilyl group and a radical polymerizable unsaturated monomer having an ultraviolet absorber component in an aqueous solution of water and an emulsifier. Radical polymerizable unsaturated monomer (c) having (b) and light stabilizer component
And at least one radical polymerizable unsaturated monomer selected from fluorine-containing radical polymerizable unsaturated monomer (d) and other radical polymerizable unsaturated monomer (e) containing radicals After producing a radical polymer (I) by performing a first stage radical emulsion polymerization reaction of the polymerizable unsaturated monomer with a radical polymerization initiator, then in the presence of the radical polymer (I), A radical polymerizable unsaturated monomer containing an alkoxysilyl group-containing radical polymerizable unsaturated monomer (a) and other radical polymerizable unsaturated monomer (e) is converted into the second stage radical emulsification. It is a core / shell type emulsion obtained by carrying out a polymerization reaction.

Examples of the alkoxysilyl group-containing polymerizable unsaturated monomer (a) include divinyldimethoxysilane, divinyldi-β-methoxyethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-β-methoxyethoxysilane, γ -Methacryloxypropyltrimethoxysilane, (gamma) -methacryloxypropyltriethoxysilane, etc. are mentioned, These may be used independently and may be used in combination of 2 or more types.

The alkoxysilyl group-containing polymerizable unsaturated monomer (a) is 1 to 40% by weight, preferably 3 to 35% by weight, based on the total monomer weight used in multiple stages (for example, two stages), More preferably, it is contained within the range of 5 to 25% by weight. If it is less than 1% by weight, the matting effect is insufficient. On the other hand, if it exceeds 40% by weight, the polymerization stability at the time of synthesis tends to decrease, and defects such as uneven gloss may occur.

In addition, the inside of the core / shell emulsion (A) is cross-linked to improve the stability of the core / shell emulsion (A), and the alkoxysilyl group is unevenly distributed outside the particles, further improving the matting effect of the coating film. Compound having two or more polymerizable unsaturated groups in one molecule (
f) may be contained in an amount of 40% by weight or less, preferably 5 to 30% by weight, based on the total monomer weight used in the first stage among the multiple stages.

Examples of the compound (f) having two or more polymerizable unsaturated groups in one molecule include allyl (
(Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1 , 4-butanediol diacrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate,
Hydroxyisocyanurate tri (meth) acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, glycerol allyloxy di (meth) acrylate, 1,1,1-tris (hydroxymethyl) ethanedi (meth) acrylate, 1,1,1-tris (hydroxymethyl) ethanetri (meth) acrylate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate, diallyl isophthalate, pentaerythritol diallyl ether, divinylbenzene, etc. It is done.

As a feature of the present invention, a radical polymerizable unsaturated monomer (b) having an ultraviolet absorber component, a radical polymerizable unsaturated monomer (c) having a light stabilizer component, and a fluorine-containing radical polymerizable unsaturated monomer. It contains at least one radically polymerizable unsaturated monomer selected from the monomer (d).

Examples of the radical polymerizable unsaturated monomer (b) having an ultraviolet absorber component include 2-
(2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole, 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2-hydroxy-4- (3-acryloyloxy- 2-Hydroxypropoxy) benzophenone, 2,2'-dihydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2,2'-hydroxy-4- (3
-Acryloyloxy-2-hydroxypropoxy) benzophenone, 2 (N-methacryloyl) aminobenzophenone and the like.
Among them, 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H
-Benzotriazole (as a commercial product, RUVA-93, manufactured by Otsuka Chemical Co., Ltd., trade name)
Is preferred.

Examples of the radical polymerizable unsaturated monomer (c) having a light stabilizer component include 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyl. Oxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2
2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6- Examples thereof include pentamethylpiperidine and 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine.

Among these, 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine (as a commercial product, FA-711MM, manufactured by Hitachi Chemical Co., Ltd., trade name) is preferable.
In addition, the following ultraviolet absorber (g) having an alcoholic hydroxyl group is added to a polyisocyanate (for example, hexamethylene diisocyanate or trimethylhexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane. Diisocyanate) through the core /
It can also introduce | transduce into this emulsion (A) by making it react with the hydroxyl group of a shell type emulsion (A).

Examples of the ultraviolet absorber (g) having an alcoholic hydroxyl group include 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (hydroxymethyl) phenol], 2,2′-. Methylenebis [6- (2H-benzotriazol-2-yl) -4
-(2-hydroxyethyl) phenol], 2,2'-methylenebis [6- (5-chloro-2H-benzotriazol-2-yl) -4- (2-hydroxyethyl) phenol]
2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (3-
Hydroxypropyl) phenol], 2,2'-methylenebis [6- (5-chloro-2H
-Benzotriazol-2-yl) -4- (3-hydroxypropyl) phenol], 2
, 2′-methylenebis [6- (5-bromo-2H-benzotriazol-2-yl) -4
-(3-hydroxypropyl) phenol], 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (2-hydroxypropyl) phenol], 2,2
'-Methylenebis [6- (5-chloro-2H-benzotriazol-2-yl) -4- (
2-hydroxypropyl) phenol], 2,2′-methylenebis [6- (5-bromo-
2H-benzotriazol-2-yl) -4- (2-hydroxypropyl) phenol]
2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (4-
Hydroxybutyl) phenol], 2,2'-methylenebis [6- (5-chloro-2H-
Benzotriazol-2-yl) -4- (4-hydroxybutyl) phenol] and the like.

Examples of the fluorine-containing unsaturated monomer (d) include perfluorobutyl ethyl acrylate, perfluoroisononyl ethyl acrylate, 2-perfluorooctyl ethyl acrylate, perfluorobutyl ethyl methacrylate, trifluoroethyl methacrylate, and perfluoroiso Nonylethyl methacrylate, 2-perfluorooctylethyl methacrylate and the like can be mentioned. Among these, 2-perfluorooctylethyl methacrylate can be mentioned as a preferable one.

Other radical polymerizable unsaturated monomers (e) include, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, (poly) ethylene glycol -Rumono (meth) acrylate, (poly) propylene glycol mono (meth) acrylate, hydroxybutyl vinyl ether, (meth) allyl alcohol, and the above hydroxyl group-containing vinyl monomers and β- Reaction products with lactone compounds such as propiolactone, dimethylpropiolactone, butyrolactone, γ-valerolactone, γ-caprolactone, γ-caprolactone, γ-lauryllactone, ε-caprolactone, δ-caprolactone, etc. For example, Plaxel FM1 (manufactured by Daicel Chemical Industries, trade name, caprolactone modified Meth) acrylic acid hydroxy esters), PLACCEL FM2 (Same as left), PLACCEL FM3 (Same as left), Placcel FA-1 (Same as left), PLACCEL FA2 (Same as left), PLACCEL FA3 (Same as left) hydroxyl group-containing unsaturated monomers such as;
For example, (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, Plaxel FM1A (hereinafter referred to as Daicel Chemical Industries, Ltd., caprolactone-modified carboxyl group-containing (meth) acrylic monomer, trade name), Plaxel FM4A, Plaxel Carboxyl group-containing unsaturated monomers such as FM10A;

For example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate,
Monomers of C1-C24 monoalcohols of acrylic acid or methacrylic acid such as butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate and lauryl methacrylate Nitrogen-containing radical polymerizations such as esters, glycidyl acrylate and radical polymerizable unsaturated monomers containing glycidyl groups, acrylonitrile, acrylamide, N-methylacrylamide, N-methylolacrylamide, N-butoxymethylacrylamide and dimethylaminoethyl methacrylate Unsaturated monomers, styrene, phenylethyl (meth) acrylate, vinyl acetate, vinyl chloride And the like, which may be used alone or two or more thereof. Other examples include crosslinkable unsaturated monomers such as allyl methacrylate and 1,6-hexanediol diacrylate.

Radical polymerizable unsaturated monomer (a) having an alkoxysilyl group described above, radical polymerizable unsaturated monomer (b) having an ultraviolet absorber component and radical polymerizable unsaturated having a light stabilizer component The blending ratio of the monomer (c), the fluorine-containing radically polymerizable unsaturated monomer (d), and the other radically polymerizable unsaturated monomer (e) is the core / shell type emulsion (A).
1 to 40% by weight, preferably 3 to 35% by weight, more preferably 3% to 35% by weight of the radically polymerizable unsaturated monomer (a) having an alkoxysilyl group, based on the total solid weight of all monomers constituting Is a radically polymerizable unsaturated monomer (b) having a proportion of 5 to 25% by weight and an ultraviolet absorber component
) And a radically polymerizable unsaturated monomer (c) having a light stabilizer component and at least one radically copolymerizable unsaturated monomer selected from a fluorine-containing radically polymerizable unsaturated monomer (d) As content, it is set to 0. 0 with respect to the total monomer weight which comprises a core / shell type emulsion (A).
01 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.5 to 5% by weight, and the content of the other radical polymerizable unsaturated monomer (e) is 40 to 90% by weight
The range of is preferable.

As the emulsifier used in the production of the core / shell type emulsion (A), a sodium salt or ammonium salt having a sulfate group, a sulfonic acid group, a phosphoric acid group, or a reactive emulsifier having these can be used. Among them, a reactive emulsifier having an ammonium salt and a polymerizable unsaturated group in the molecule can be suitably used for the reason that the matte effect is good and the coating film performance is excellent.

The amount of the emulsifier is preferably in the range of 0.5 to 5% by weight based on the total polymerizable unsaturated monomer used in multiple stages for the production of the core / shell type emulsion (A). Further, usable polymerization initiators include potassium persulfate, sodium persulfate, ammonium persulfate, 4,4′-
Organic azo compounds such as azobis (4-cyanovaleric acid), 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], benzoyl peroxide, di-t-butyl hydroper And organic peroxides such as oxides.

Moreover, it is also possible to use a redox initiator together with these. These polymerization initiators are
The core / shell emulsion (A) is preferably used in the range of 0.1 to 1.0% by weight based on the total polymerizable unsaturated monomer used in multiple stages.

For the production of the core / shell type emulsion (A), a radically polymerizable unsaturated monomer (a) having an alkoxysilyl group and a radically polymerizable unsaturated monomer having an ultraviolet absorber component are used in an aqueous solution of water and an emulsifier. Radical polymerizable unsaturated monomer (c) having a monomer (b) and a light stabilizer component
), A radical copolymerizable unsaturated monomer containing other radical polymerizable unsaturated monomer (d) in the presence of a radical polymerization initiator as a first stage radical polymerization reaction, for example, 1 ~
A radical emulsion polymerization reaction is performed at 90 to 110 ° C. for 2 hours to obtain the radical polymer (I).
Next, in the presence of the radical polymer (I), the second stage radical emulsion polymerization reaction is carried out at 90 to 110 ° C. for 1 to 2 hours to perform the core emulsion (A).
Get.
The radical polymerizable unsaturated monomer (a) having an alkoxysilyl group used for the second stage radical emulsion polymerization reaction and the other radical polymerizable unsaturated monomer (e) The same monomers as those used in the above can be used.
The hydroxyl value of the core / shell type emulsion (A) is 5 to 100 mgKOH / g, and the average particle diameter (Note 1) is 0.05 to 0.5 μm, preferably 0.1 to 0.3 μm.

  Average particle diameter: measured using a Coulter Counter N4 (trade name, manufactured by Coulter).

Acrylic resin (B):
Examples of the acrylic resin (B) include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, (poly)
Ethylene glycol mono (meth) acrylate, (poly) propylene glycol mono (meth) acrylate, hydroxybutyl vinyl ether, (meth) allyl alcohol, and hydroxyl group-containing vinyl monomers described above Reaction products with lactone compounds such as β-propiolactone, dimethylpropiolactone, butyrolactone, γ-valerolactone, γ-caprolactone, γ-caprolactone, γ-lauryllactone, ε-caprolactone, and δ-caprolactone As a trade name, Plaxel FM1 (manufactured by Daicel Chemical Industries, trade name, caprolactone-modified (meth) acrylic acid hydroxyesters), Plaxel FM2 (same as left), Plaxel FM3 (same as left), Plaxel FA-1 (same as left), Plaxel FA2 (same as left), Plaxel FA3 (same as left), etc. Hydroxyl group-containing unsaturated monomer;
For example, (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, Plaxel FM1A (hereinafter referred to as Daicel Chemical Industries, Ltd., caprolactone-modified carboxyl group-containing (meth) acrylic monomer, trade name), Plaxel FM4A, Plaxel Carboxyl group-containing unsaturated monomers such as FM10A;

In addition, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl Monoesters of acrylic acid or methacrylic acid such as acrylate and lauryl methacrylate with monoalcohols having 1 to 24 carbon atoms, glycidyl acrylate and radical polymerizable unsaturated monomers containing glycidyl groups, acrylonitrile, acrylamide, N- Methyl acrylamide, N-methylol acrylamide, N-butoxymethyl acrylic Nitrogen-containing radical-polymerizable unsaturated monomers, such as bromide and dimethylaminoethyl methacrylate, styrene, phenyl ethyl (meth) acrylate,
Examples include vinyl acetate and vinyl chloride.

These can be used alone or in combination of two or more. Other examples include crosslinkable unsaturated monomers such as allyl methacrylate and 1,6-hexanediol diacrylate, polymerized products, and the like. The hydroxyl value of the acrylic resin (B) is 20 to 200 mgKOH /
g, an acid value of 20 to 200 mgKOH / g, and a weight average molecular weight of 3,000 to 10,000 are preferable.

Curing agent (C): Curing agent (C) consists of core / shell emulsion (A), acrylic resin (
In order to react with the hydroxyl group of B) and obtain a crosslinked coating film, a melamine resin and / or block polyisocyanate can be used conveniently.

As the melamine resin, for example, those modified with one or more alcohols such as methanol, ethanol, propanol, butanol, octyl alcohol, 2-ethylhexyl alcohol and the like can be used. Preferably C3 or higher, especially C4-18
Those modified with alcohols are preferred. The average number of ether groups modified with an alcohol of C3 or higher in the melamine resin is about 2.0 or more, especially about 2 per triazine ring.
. It is preferable to contain 0-5.0 pieces.

As isocyanate used for block polyisocyanate, what is known conventionally can be used, for example, tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4 , 4'-diisocyanate (usually called "MDI"), crude MDI, bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, isophorone diisocyanate, aromatic, aliphatic or alicyclic polyisocyanates Compound;
Cyclic polymers of these polyisocyanate compounds, isocyanate violets; low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, trimethylolpropane, hexanetriol, castor oil and the like in excess of these polyisocyanate compounds The terminal isocyanate containing compound obtained by making it react can be mentioned. These can be used alone or in combination of two or more.

On the other hand, the blocking agent is added and blocked to the isocyanate group of the polyisocyanate compound, and the blocked polyisocyanate compound produced by the addition is stable at room temperature, but the baking temperature of the coating film (usually about 100 to When heated to about 200 ° C., it is desirable that the blocking agent dissociates and free isocyanate groups can be regenerated.

Examples of the blocking agent that satisfies such requirements include lactam compounds such as ε-caprolactam and γ-butyrolactam; oxime compounds such as methyl ethyl ketoxime and cyclohexanone oxime; phenols such as phenol, para-t-butylphenol, and cresol. Compounds; aliphatic alcohols such as n-butanol and 2-ethylhexanol; aromatic alkyl alcohols such as phenyl carbinol and methyl phenyl carbinol; ether alcohol compounds such as ethylene glycol monobutyl ether and diethylene glycol monoethyl ether Can be mentioned.

About anionic electrodeposition paints:
In the anionic electrodeposition coating composition of the present invention, the blending ratio of the core / shell type emulsion (A), the acrylic resin (B), and the curing agent (C) is preferably 1 to 40% by weight of the core / shell type emulsion (A). Is 5 to 20 wt%, acrylic resin (B) is 20 to 70 wt%, preferably 3
It is suitable that the content is 0 to 60% by weight and the curing agent (C) is within the range of 20 to 60% by weight, preferably 30 to 50% by weight.

The anionic electrodeposition paint of the present invention includes a curing catalyst such as an organic tin compound, a pigment, a filler, an aggregate,
A pigment dispersant, a wetting agent, an antifoaming agent, a plasticizer, an organic solvent, an antiseptic, a mildew-proofing agent, a pH adjuster, a rust-proofing agent, and the like can be appropriately selected according to each purpose, and can be combined. .

As an object to be coated, it is applied to a metal material such as aluminum, aluminum alloy, anodized, steel; plated steel plate plated with zinc, tin, chromium, aluminum, etc .; or steel plate subjected to chemical conversion treatment or cathodic electrolytic treatment with chromic acid or phosphoric acid it can. In particular, it is desirable to apply to the field of aluminum building materials using a colored or uncolored anodized aluminum material.

Examples of the coating method include an anionic electrodeposition paint bath (for example, a solid content of about 5 to 20% by weight,
Preferably, the aluminum material is immersed in this bath, and then anion electrodeposition coating is performed so that the dry film thickness is about 5 to 30 μm, followed by washing with water as necessary (tap water) , Permeated water, etc.) followed by baking (for example, at about 160 to 200 ° C. for about 20 to 40 minutes).

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited thereby. “Parts” and “%” indicate “parts by weight” and “% by weight”.
Production Example 1 Emulsion No. A reaction vessel equipped with 1 production thermometer, thermostat, stirrer, reflux condenser, and dropping device was charged with 298 parts of deionized water and heated to 90 ° C. Thereafter, an initiator aqueous solution consisting of 0.15 parts of VA-086 (Note 2) and 9.85 parts of deionized water was added to the reaction vessel and stirred for 15 minutes.
In a separate container
SE-10N (Note 3) 1 part
30 parts of deionized water
20 parts of styrene
17 parts of n-butyl acrylate
2-hydroxyethyl acrylate 2 parts 1,6-hexanediol diacrylate 5 parts
KBM-503 (Note 4) 4 parts RUVA-93 (Note 5) 2 parts.
Was mixed to prepare a monomer emulsion (1), which was dropped into the reaction vessel over 2 hours.
Simultaneously with the start of dropping of the monomer emulsion (1), an initiator aqueous solution consisting of 1 part of “VA-086” (Note 2) and 30 parts of deionized water is 5.5 until the completion of all steps including the reaction described below. It was dripped at reaction container over time. 30 minutes after the completion of dropping of the monomer emulsion (1), it was prepared in a separate container.
SE-10N (Note 3) 1 part Deionized water 30 parts
15 parts of styrene
13 parts of n-butyl acrylate
2-hydroxyethyl acrylate 4 parts 1,6-hexanediol diacrylate 3 parts
KBM-503 (Note 4) 15 parts
A monomer emulsion (2) consisting of 2 is added dropwise over 2 hours and then aged for 1 hour.
Emulsion No. 0% with an average particle size of 127 μm. 1 was obtained.
(Note 2) VA-086: manufactured by Wako Pure Chemical Industries, Ltd., trade name, nonionic water-soluble polymerization initiator, 2,
2'-Azobis [2-methyl-N- (2-hydroxyethyl) propionamide]
(Note 3) SE-10N: Asahi Denka Co., Ltd., trade name, ammonium sulfate-based reactive emulsifier (Note 4) KBM-503: Shin-Etsu Chemical Co., Ltd., trade name, γ-methacryloyloxypropyltrimethoxysilane.
(Note 5) RUVA-93: manufactured by Otsuka Chemical Co., Ltd., trade name, 2- (2′-hydroxy-5′-
Methacryloyloxyethylphenyl) -2H-benzotriazole (Note 6) FA-711MM: Hitachi Chemical Co., Ltd., trade name, 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine (Note 7) FAMAC: Nippon Mektron, trade name, 2-perfluorooctylethyl methacrylate.

Production Examples 2-6
Except for the formulation shown in Table 1, the same procedure as in Production Example 1 was carried out. 2-No. 6 was obtained.

Production Example 7 Production of acrylic resin (B) Thermometer, thermostat, stirrer, reflux condenser, and reaction vessel equipped with dropping device, 100 parts isopropyl alcohol, 150 parts n-butyl alcohol, butyl cellosolve 100
The temperature was raised to 85 ° C. and a mixture of the following monomers was added dropwise over 3 hours. After that, 5 parts of azobisdimethylvaleronitrile was placed in a reaction vessel and kept at 85 ° C. for 3 hours. The solid content was adjusted with a solvent to obtain an acrylic resin solution having an acid value of 46 mgKOH / g, a hydroxyl value of 67 mgKOH / g, a weight average molecular weight of about 50,000, and a solid content of 60%.
Styrene 50 parts methyl methacrylate 200 parts n-butyl acrylate 100 parts ethyl acrylate 50 parts 2-hydroxyethyl acrylate 70 parts acrylic acid 30 parts azobisdimethylvaleronitrile 4 parts.

Example 1
45 parts of acrylic resin solution obtained in Production Example 7 (in solid content), Nicalac MX-430 (Note 8)
40 parts (in terms of solid content), 0.4 equivalent of triethylamine is blended with respect to the carboxyl group of the acrylic resin, and deionized water is added so that the resin solid content becomes 10% while mixing and dispersing the mixture. Dropped and dispersed in water.
Emulsion No. obtained in Production Example 1 was obtained. 15 parts (in terms of solid content) of 1 was added, and further an amount that neutralized 0.4 equivalents of triethylamine was added to adjust the pH to 8.2 and the resin solid content to 10%. No. 1 was obtained.

Examples 2-5
In the contents of Table 2, the anion electrodeposition paint Nos. 2 to 5 of Examples 2 to 5 were prepared in the same manner as in Example 1. 2 to
5 was obtained.

Comparative Examples 1-3
In the contents of Table 2, the anion electrodeposition paint Nos. 1 to 3 of Comparative Examples 1 to 3 were prepared in the same manner as in Example 1. 6 ~
8 was obtained.

（注８）ニカラックＭＸ−４３０：三和ケミカル社製、商品名、メラミン核１個当たりメ
チル基約３個、ブチル基約３個で１核体の量は約５７％のメラミン樹脂、固形分１００％
。

(Note 8) Nicarax MX-430: Sanwa Chemical Co., Ltd., trade name, about 3 methyl groups and about 3 butyl groups per melamine nucleus and about 57% melamine resin, solid content 100%
.

(Note 9) Duranate TPA-B80: manufactured by Asahi Kasei Corporation, trade name, hexamethylene diisocyanate isocyanurate type, methyl ethyl ketoxime block.

(Note 10) SCAT-7: trade name, dibutyltin bismercaptocarboxylate ester, curing catalyst, manufactured by Sansha Co., Ltd.

  (Note 11) Tinuvin 328: Ciba Geigy Co., Ltd., trade name, UV absorber.

  (Note 12) Tinuvin 292: manufactured by Ciba Geigy Corp., trade name, light stabilizer.

Preparation of test plates Anion electrodeposition paint obtained in Examples and Comparative Examples was used as a bath, and this was anodized (
An anodic oxidized aluminum material (silver: size: 150 × 70 × 0.5 mm) having an oxidized film thickness of about 10 μm subjected to degreasing-etching-neutralization-anodizing treatment-sealing) is immersed in a dry film thickness. Electrodeposition coating was performed to 10 μm, washed with water, and baked at 180 ° C. for 20 minutes.

  The test was conducted according to the following test conditions. The test results are shown in Table 3.

(Note 13) Paint stability: Filled in a paint test tube (height 20 cm, capacity 20 ml), 20 ° C.
Then, the height of the residue precipitated on the bottom of the test tube was measured.
Rating:
○: Residue is less than 0.5 mm, good
Δ: Residue is slightly poor at 0.5 to 3 mm
X: Residue is 3 mm or more, which is poor.

(Note 14) Weather resistance (gloss retention): 18 hours irradiation (irradiation intensity: 80 mW / day) using a metal halide lamp type super accelerated weathering tester (manufactured by Daipura Wintes Co., Ltd .: Metal Weather)
cm ² ) and 6 hours of condensation as one cycle (24 hours), a 15 cycle (360 hours) test was conducted. The gloss retention rate (%) was expressed as a percentage of the glossiness after the test when the glossiness before the test was 100 according to the 60-degree specular glossiness specified in JIS K-8741.

(Note 15) Weather resistance (color difference ΔE): The coating film before and after irradiation with a metal halide lamp type super accelerated weathering tester was measured using a color difference meter (manufactured by Konica Minolta: CR-300).
ΔE calculated using the L ^* a ^* b ^* color system of IS Z 8730 6.1 was determined.

(Note 16) Weather resistance (adhesiveness): Lines reaching 11 coatings in length and width at 1 mm intervals on the coating surface of the test plate using a cutter knife blade in accordance with JIS H-8602 5.8 To make 100 grids. On top of this, a 12 mm width tape specified in JIS Z 1522 is strongly pressed with a finger and is peeled off immediately in the direction immediately after being applied ○ is 100 (remaining number) / 100 △ is 95 to 99 Pieces (remaining number) / 100 pieces x is less than 95 pieces (remaining number) / 100 pieces.

(Note 17) Pencil hardness: about 4 with respect to the test coated plate surface in accordance with JIS H-8602 5.9
The pencil lead was applied at an angle of 5 degrees, and it was moved forward about 10 mm at a uniform speed while pressing against the surface of the test coating plate so strongly that the lead did not break. This operation was repeated 5 times at different test locations, and the pencil hardness symbol when the coating film was not torn 4 times was defined as pencil hardness.

(Note 18) 60 ° gloss:
The degree of gloss of the coating film is measured according to the 60 degree specular gloss specified in JIS K-8741, and the reflectance when the incident angle and the light receiving angle are 60 degrees is measured. Expressed as a percentage when the glossiness is 100.

(Note 19) Dice mark concealment:
Evaluation was made by visual evaluation.
○ indicates good dice mark concealment,
△ is inferior in dice mark concealment,
X is remarkably inferior in dice mark concealment.

  Since the present invention is excellent in dice mark concealing properties, it is effectively used for coating aluminum molds widely used for building materials and the like.

Claims (6)

An emulsion polymer produced by emulsion polymerization in multiple stages using a polymerizable unsaturated monomer in the presence of water and an emulsifier, wherein the polymerizable polymer contains an alkoxysilyl group and is polymerizable. Contains a core / shell type emulsion (A), acrylic resin (B), and curing agent (C) containing 1 to 40% by weight of unsaturated monomers in a total amount of monomers used in multiple stages Anion electrodeposition paint that
The core / shell type emulsion (A) is a radical polymerizable unsaturated monomer having an alkoxysilyl group (a) and a radical polymerizable unsaturated monomer having an ultraviolet absorber component in an aqueous solution of water and an emulsifier ( At least one radical polymerizable unsaturated monomer selected from b), a radical polymerizable unsaturated monomer (c) having a light stabilizer component and a fluorine-containing radical polymerizable unsaturated monomer (d) And other radically polymerizable unsaturated monomer (e), and if necessary, a radically polymerizable unsaturated monomer containing monomer (f) containing two or more unsaturated groups in one molecule After producing the radical polymer (I) by performing the first stage radical emulsion polymerization reaction in the presence of a radical polymerization initiator,
Next, in the presence of the above-mentioned radical polymer (I), a radical polymerizable unsaturated monomer (a) having an alkoxysilyl group and other radical polymerizable unsaturated monomers (e), 1 if necessary A core / shell type emulsion obtained by subjecting a radical polymerizable unsaturated monomer containing a monomer (f) containing two or more unsaturated groups in the molecule to a second stage radical emulsion polymerization reaction An anionic electrodeposition paint characterized by  The core / shell type emulsion (A) comprises a radical polymerizable unsaturated monomer (b) having an ultraviolet absorber component, a radical polymerizable unsaturated monomer (c) having a light stabilizer component, and fluorine-containing radical polymerization. At least one radically polymerizable unsaturated monomer selected from the polymerizable unsaturated monomers (d) is 0.01% with respect to the total monomer weight constituting the core / shell emulsion (A). The anionic electrodeposition coating material according to claim 1, wherein the anionic electrodeposition coating material is contained at a ratio of 10 wt% to 10 wt%.   The radically polymerizable unsaturated monomer (b) having an ultraviolet absorber component includes 2- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole. Or an anionic electrodeposition paint described in 2.   The radically polymerizable unsaturated monomer (c) having a light stabilizer component contains 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine. Anion electrodeposition paint described in 1.   The anion electrodeposition coating material according to claim 1 or 2, characterized in that it contains 2-perfluorooctylethyl methacrylate as the fluorine-containing radically polymerizable unsaturated monomer (d).   A cured coating film obtained by electrodeposition-coating the anion electrodeposition coating composition according to any one of claims 1 to 5 on a material to be coated has a 60-degree specular gloss as defined in JIS K-8741. Painted article whose is 30 or less.