Coating agent

Abstract

To provide a coating agent which exhibits stable recoatability and provides an aesthetically excellent coating finish by securing concealability.SOLUTION: There is provided a coating agent containing a resin component (A), a pigment (B), an organometallic compound (C) and an aliphatic hydrocarbon-containing non-aqueous solvent (D), wherein the coating agent contains a non-aqueous dispersion type resin (A-1) and a soluble type resin (A-2) as the resin component (A), in which the non-aqueous dispersion type resin (A-1) and / or the soluble type resin (A-2) have an oxidatively polymerizable group and an acid value and contains surface-treated rutile type titanium dioxide (B-1) as the pigment (B) and the total oil absorption of the pigment (B) is 60 g or less based on 100 g of the solid content of the above resin component (A).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a novel coating agent.

Background Art

[0002] Conventionally, in buildings, civil engineering structures, etc., for the purpose of protecting the base material and improving the aesthetics, finishing with various coating agents has been carried out. In recent years, in the field of such coating agents, there has been an increasing movement to suppress the use of aromatic hydrocarbon solvents such as toluene and xylene in consideration of safety during painting, work hygiene, or the impact on air pollution. In order to respond to such a movement, various environmentally friendly coating agents using aliphatic hydrocarbon solvents have been proposed.

[0003] As such an environmentally friendly coating agent, those using an oxidation-curing type resin are known. For example, Japanese Patent Application Laid-Open No. 2004-352764 (Patent Document 1) describes a coating agent containing a resin component derived from an unsaturated fatty acid, a metal drier, a specific titanium oxide, etc. The coating agent described in the publication causes a cross-linking reaction by the oxidation of reactive double bonds contained in the unsaturated fatty acid, and a metal drier is used as its curing catalyst.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] In the coating agent as described above, by using a pigment with a high refractive index such as titanium oxide, hiding power is imparted, and it is possible to prevent the substrate to be painted from being seen through. However, when performing a coating finish with such a coating agent, especially on a vertical surface such as a wall surface or an inclined surface such as a roof, if an attempt is made to ensure hiding power with a single coating, there is a risk of sagging or the like, so it may be finished by applying two or more coats.

[0006] However, during such multiple coatings, since there is almost no absorption into the substrate, there is a tendency for sagging or the like to occur more easily than during the first coating, and there is also a risk of problems such as lifting. Such problems will have an adverse effect on the finish. On the other hand, when the formed finish film becomes dirty or damaged, it may be repaired by multiple coatings, but there is also a risk of the same problems occurring at this time.

[0007] The present invention has been made in view of such points, and an object thereof is to provide a coating agent that exhibits stable recoating suitability, ensures hiding power, and can perform a coating finish with excellent aesthetic properties.

Means for Solving the Problems

[0008] In order to solve such problems, as a result of intensive studies, the inventors of the present invention have conceived that in order to suppress the occurrence of problems during recoating as described above and to exhibit stable recoating suitability, it is effective to specify the composition of the resin component and the pigment component, and have completed the present invention.

[0009] That is, the present invention has the following features. 1. A coating agent containing a resin component (A), a pigment (B), an organometallic compound (C), and an aliphatic hydrocarbon-containing non-aqueous solvent (D), The resin component (A) includes a non-aqueous dispersion resin (A-1) and a soluble resin (A-2), The non-aqueous dispersion resin (A-1) and / or the soluble resin (A-2) has an oxidative polymerizable group, The above non-aqueous dispersion resin (A-1) and The above soluble resin (A-2) has an acid value, the acid value is 0.3 to 30 mgKOH / g, As the above pigment (B), it contains surface-treated rutile-type titanium oxide (B-1), When based on 100 g of the solid content of the above resin component (A), the total oil absorption of the above pigment (B) is 60 g or less, the surface-treated rutile-type titanium oxide (B-1) has an oil absorption of 30 g / 100 g or less and a TiO 2 content of 80 to 89% and As the above organometallic compound (C), it contains an organometallic compound (C-1) containing one or more metals selected from the group consisting of cobalt, manganese, vanadium, cerium, and iron, and an organometallic compound (C-2) containing one or more metals selected from the group consisting of zirconium, bismuth, aluminum, strontium, titanium, zinc, barium, copper, and calcium. The weight ratio {(C-1):(C-2)} of the (C-1) component to the (C-2) component is 1:99 to 50:50 in terms of metal conversion, A coating agent characterized by the above.

Effect of the Invention

[0010] The coating agent of the present invention exhibits stable overcoating suitability, ensures hiding power, and can perform a coating finish with excellent aesthetic properties.

Embodiments for Carrying Out the Invention

[0011] Hereinafter, embodiments for carrying out the present invention will be described.

[0012] The coating agent of the present invention contains a resin component (A), a pigment (B), an organometallic compound (C), and an aliphatic hydrocarbon-containing non-aqueous solvent (D).

[0013] In the coating agent of the present invention, as the resin component (A) (hereinafter also referred to as the “(A) component”), a non-aqueous dispersion resin (A-1) (hereinafter also referred to as the “(A-1) component”) and a soluble resin (A-2) (hereinafter also referred to as the “(A-2) component”) are included. One or both of the (A-1) component and the (A-2) component have an oxidation polymerizable group, and further one or both of the (A-1) component and the (A-2) component have an acid value. In the present invention, the combined use of the non-aqueous dispersion resin (A-1) and the soluble resin (A-2) contributes to the improvement of the suitability for overcoating and the like. Specifically, by the combined use of the non-aqueous dispersion resin (A-1) and the soluble resin (A-2), the occurrence of dripping and the like during overcoating can be suppressed, and the finishability can be enhanced. When applied to a coating agent containing a coloring pigment, it is advantageous in terms of improving the pigment miscibility and the finishability during overcoating. When applied to a glossy coating agent, it is also advantageous in terms of improving the gloss and the like.

[0014] The non-aqueous dispersion resin (A-1) has both a resin portion soluble in the aliphatic hydrocarbon-containing non-aqueous solvent (D) and a resin portion insoluble therein, and is dispersed in the non-aqueous solvent (D) in the form of resin particles. The (A-1) component can be obtained, for example, by polymerizing various vinyl monomers in a conventional manner in the presence of a resin soluble in the non-aqueous solvent (D). The weight average molecular weight of the (A-1) component is preferably 10,000 to 500,000, more preferably 20,000 to 300,000. The glass transition temperature of the (A-1) component is preferably -5°C to 70°C, more preferably 10°C to 60°C. The glass transition temperature is a value obtained by the Fox calculation formula based on the vinyl monomers constituting the resin. In the present invention, “a to b” has the same meaning as “a or more and b or less”.

[0015] The soluble resin (A-2) is a resin that can be dissolved in an aliphatic hydrocarbon-containing non-aqueous solvent (D). The component (A-2) can be obtained, for example, by polymerizing various vinyl monomers in the above non-aqueous solvent (D) by a conventional method. From the viewpoints of recoatability, workability and finish during coating, durability of the coating film, etc., the weight average molecular weight of the component (A-2) is preferably 2,000 to 300,000, more preferably 10,000 to 250,000, still more preferably 30,000 to 220,000, and particularly preferably 50,000 to 200,000. The glass transition temperature of the component (A-2) is preferably -5°C to 70°C, more preferably 10°C to 60°C.

[0016] The solid content weight ratio of the component (A-1) to the component (A-2) {(A-1) component / (A-2) component} is preferably 98 / 2 to 20 / 80, more preferably 95 / 5 to 40 / 60, still more preferably 90 / 10 to 50 / 50.

[0017] In the component (A) of the present invention, the component (A-1) and / or the component (A-2) has an oxidation polymerizable group. That is, one or both of the component (A-1) and the component (A-2) has an oxidation polymerizable group. Thereby, the component (A) is air-oxidized and cured and dried by an oxidation polymerizable double bond (oxidation polymerizable group). In the present invention, from the viewpoints of curability, durability, etc., it is desirable that at least the component (A-1) has an oxidation polymerizable group, and it is more desirable that both the component (A-1) and the component (A-2) have an oxidation polymerizable group. To impart an oxidation polymerizable group to the component (A-1) and / or the component (A-2), for example, the following resins may be used.

[0018] 1) A resin obtained by copolymerizing a vinyl monomer having an oxidation polymerizable group and another vinyl monomer copolymerizable with this monomer. 2) A resin obtained by copolymerizing an epoxy group-containing vinyl monomer and another vinyl monomer copolymerizable with this monomer, and then adding an unsaturated fatty acid to the epoxy group-containing vinyl monomer. 3) A resin obtained by copolymerizing and / or graft copolymerizing a vinyl monomer having an oxidation-polymerizable group and / or another vinyl monomer copolymerizable with this monomer with an alkyd resin.

[0019] Examples of the vinyl monomer having an oxidation-polymerizable group in the above 1) and 3) include vinyl monomers obtained by adding an unsaturated fatty acid to an epoxy group-containing vinyl monomer. This vinyl monomer is obtained by the reaction of an epoxy group and a carboxyl group in an unsaturated fatty acid. Further, the resin of the above 2) is obtained by the addition reaction of an unsaturated fatty acid to an epoxy group in the resin. When reacting an epoxy group and an unsaturated fatty acid, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used.

[0020] Specific examples of the epoxy group-containing vinyl monomer include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 3,4-oxycyclohexylpropyl (meth)acrylate, allyl glycidyl ether, and the like. These can be used alone or in combination of two or more.

[0021] Examples of the unsaturated fatty acid include linseed oil fatty acid, tung oil fatty acid, fish oil fatty acid, dehydrated castor oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, poppy oil fatty acid, eno oil fatty acid, safflower oil fatty acid, hemp seed oil fatty acid, grape seed oil fatty acid, tall oil fatty acid, sunflower oil fatty acid, cottonseed oil fatty acid, corn oil fatty acid, walnut oil fatty acid, and the like. These can be used alone or in combination of two or more. The composition ratio of the unsaturated fatty acid in the component (A-1) and / or the component (A-2) is preferably 0.5 to 40% by weight, more preferably 1 to 35% by weight, still more preferably 3 to 30% by weight, based on the resin solid content of the component (A-1) or the component (A-2), from the viewpoints of curability, recoatability, etc.

[0022] As the vinyl monomer having an oxidative polymerizable group in the above 1) and 3), for example, a dicyclopentadiene oxyalkyl group-containing vinyl monomer such as dicyclopentadiene oxyalkyl (meth) acrylate, or an allyl group-containing vinyl monomer such as allyl (meth) acrylate can also be used. These can be used alone or in combination of two or more.

[0023] As the alkyd resin in the above 3), those obtained by polycondensing a polyhydric alcohol and a polyvalent carboxylic acid and modifying the product with a drying oil, an unsaturated fatty acid, etc. can be used. Among these, examples of the polyhydric alcohol include ethylene glycol, glycerin, pentaerythritol, etc., and examples of the polyvalent carboxylic acid include phthalic anhydride, maleic anhydride, etc. Examples of the drying oil include linseed oil, tung oil, oiticica oil, safflower oil, etc.

[0024] Examples of the other vinyl monomers in the above 1) to 3) include (meth)acrylic acid alkyl esters, aromatic monomers, and the like. Among these, specific examples of the (meth)acrylic acid alkyl ester include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, and the like. Specific examples of the aromatic monomer include, for example, styrene, 2-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, vinyl anisole, vinyl naphthalene, divinylbenzene, and the like. These can be used alone or in combination of two or more. As such vinyl monomers, for example, carboxyl group-containing vinyl monomers, amino group-containing vinyl monomers, hydroxyl group-containing vinyl monomers, and the like can also be used. As the component (A), as other monomers, those in which at least a (meth)acrylic acid alkyl ester is copolymerized, those in which a (meth)acrylic acid alkyl ester and an aromatic monomer are copolymerized, and the like are preferable.

[0025] (A-1) component and / or (A-2) component have an acid value. In the present invention, by using such a resin component having an acid value, the curability can be improved and the suitability for overcoating can be enhanced. Furthermore, the improvement of pigment miscibility and the like can also be achieved, which is advantageous in terms of finish and the like. The acid value of the resin component is preferably 0.1 to 50 mgKOH / g, more preferably 0.3 to 30 mgKOH / g, and still more preferably 0.5 to 20 mgKOH / g based on the resin solid content of the (A-1) component or (A-2) component. In the present invention, it is desirable that both the (A-1) component and the (A-2) component have the above acid value. The acid value is a value represented by the number of mg of potassium hydroxide equimolar to the acid groups contained in 1 g of the resin solid content. To set the acid value of the resin within the above range, for example, a vinyl monomer containing a carboxyl group or the like may be used as the other vinyl monomer in the above 1) to 3). Examples of the vinyl monomer containing a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, maleic acid or its monoalkyl ester, itaconic acid or its monoalkyl ester, fumaric acid or its monoalkyl ester, ω-carboxy-polybutyrolactone mono(meth)acrylate, ω-carboxy-polyvalerolactone mono(meth)acrylate, ω-carboxy-polycaprolactone mono(meth)acrylate, ω-carboxy-polycaprylolactone mono(meth)acrylate, ω-carboxy-poly lauryllactone mono(meth)acrylate, (meth)acrylic acid dimer, (meth)acrylic acid trimer, (meth)acrylic acid tetramer, (meth)acrylic acid heptamer, (meth)acrylic acid hexamer, and the like. These can be used alone or in combination of two or more.

[0026] (A-1) component and / or (A-2) component may have an amine value, a hydroxyl value, etc. The amine value in the (A-1) component and / or (A-2) component is preferably 20 mgKOH / g or less, more preferably 0.01 to 10 mgKOH / g, based on the resin solid content of the (A-1) component or (A-2) component. The hydroxyl value in the (A-1) component and / or (A-2) component is preferably 100 mgKOH / g or less, more preferably 1 to 80 mgKOH / g, still more preferably 2 to 50 mgKOH / g, particularly preferably 3 to 30 mgKOH / g, based on the resin solid content of the (A-1) component or (A-2) component. In the present invention, in terms of improving gloss, improving finish properties, etc., it is desirable that at least the (A-2) component has the above amine value and / or hydroxyl value.

[0027] As the (A-1) component and / or (A-2) component, those obtained by modifying the above-mentioned resin with, for example, an isocyanate compound, a urethane compound, a silicone compound, an alkoxysilane compound, etc. can also be used.

[0028] The pigment (B) (hereinafter also referred to as the "(B) component") is a component that imparts color to the coating agent of the present invention and further imparts hiding properties, etc. In the present invention, as the pigment (B), at least surface-treated rutile-type titanium oxide (B-1) (hereinafter also referred to as the "(B-1) component") is included. And the total oil absorption amount of the pigment (B) (when based on 100 g of the solid content of the resin component (A)) is set to be 60 g or less. In the present invention, when the pigment (B) has a configuration that satisfies such conditions, stable overcoating suitability can be exhibited, and a coating finish with excellent aesthetic properties can be achieved.

[0029] The reason for such an effect is not restricted by the following theory, but titanium oxide has the property of generating radicals, and those radicals may act on the oxidative polymerizable groups of the resin component (A) and inhibit the curing by the organometallic compound (C). Also, if the total oil absorption amount of the pigment (B) is too large, the organometallic compound (C) is likely to be adsorbed by the pigment (B), and the curing by the organometallic compound (C) becomes difficult to proceed.

[0030] In contrast, in the present invention, by satisfying the condition that the pigment (B) satisfies the above conditions, that is, by using the specific titanium oxide (B-1) and controlling the total oil absorption amount of the pigment (B), the curing of the resin component (A) by the organometallic compound (C) proceeds stably. Further, the curing action of the organometallic compound (C) is sufficiently exerted by the acid groups of the resin component (A). Thereby, lifting during overcoating is suppressed, the overcoating suitability becomes good, and it is considered that a coating finish state excellent in aesthetic appearance can be obtained.

[0031] The surface-treated rutile-type titanium oxide (B-1) plays a role as a white pigment and contributes to overcoating suitability and the like. In untreated rutile-type titanium oxide and anatase-type titanium oxide, radicals are likely to be generated, and the radicals inhibit the curing by the organometallic compound (C), promote the occurrence of lifting, and have an adverse effect on overcoating suitability. In the present invention, the titanium oxide may be substantially composed mainly of TiO2, and may contain some impurities (for example, antimony oxide, niobium oxide, potassium oxide, phosphorus oxide, sulfur oxide, etc.).

[0032] As the component (B-1), those in which the surface of rutile-type titanium oxide particles is surface-treated with at least an inorganic compound can be used. Examples of the inorganic compound used for the surface treatment include silica, alumina, zirconia, titania, tin oxide, antimony oxide, zinc oxide, etc. Among these, an embodiment containing one or more selected from the group consisting of silica, alumina, and zirconia is preferable. In addition to these, the inorganic compound may also contain, for example, compounds containing phosphorus, calcium, magnesium, strontium, barium, etc. The surface treatment with such an inorganic compound can be carried out by a known method. For example, an aqueous salt solution of Si, Al, Zr, Ti, Sn, Sb, Zn, etc. is added to a slurry containing titanium oxide, and an alkali or acid for neutralizing this is added to generate a hydrous oxide on the surface of the titanium oxide particles, and then processes such as filtration, drying, and pulverization can be adopted.

[0033] In addition, the component (B-1) may be surface-treated with an organic compound in addition to the above inorganic compound. Examples of the organic compound used for the surface treatment include fatty acids, fatty acid esters, surfactants, metal soaps, silicone resins, fluororesins, acrylic resins, polyester resins, silane coupling agents, titanium coupling agents, waxes, and the like. These can be used alone or in combination of two or more. The surface treatment with such an organic compound can be carried out by a known method. For example, a method of adding and mixing an organic compound before or after drying in the surface treatment method with the above inorganic compound can be adopted.

[0034] The oil absorption amount of the component (B-1) is preferably 30 g / 100 g or less. With such an oil absorption amount, the surface of the titanium oxide particles is likely to be in a state where it is densely surface-treated with the above inorganic compound or the like, which is advantageous for suppressing radical generation and also for suppressing the adsorption of the organometallic compound (C). It is suitable from the viewpoint of improving the effects of the present invention. The lower limit of the oil absorption amount of the component (B-1) is not particularly limited, but is preferably 5 g / 100 g or more. If the lower limit of the oil absorption amount is such a value, it is suitable in terms of imparting viscosity, coating workability, finish, etc. The oil absorption amount is a value measured by the method of JIS K5101-13-2:2004.

[0035] (B-1) component of TiO 2 The content is preferably 95% or less, more preferably 90% or less, and still more preferably 80 to 89%. If the TiO 2 content of the component (B-1) is within such a range, the surface treatment is likely to be in a thicker state, which is advantageous for suppressing radical generation and is suitable from the viewpoint of improving the effects of the present invention. The TiO2 content is a value (mass fraction) measured by JIS K5116:2004 7.2.

[0036] In the present invention, by including a coloring pigment (B-2) (hereinafter also referred to as the “(B-2) component”) as the component (B), it becomes possible to exhibit various colors. As the (B-2) component, a colored pigment, a black pigment, etc. can be used. Among these, the colored pigment is, for example, a pigment that exhibits a color such as yellow, orange, red, green, blue, purple, etc. Examples of such colored pigments include inorganic ones such as ferric oxide, hydrated ferric oxide, ultramarine, cobalt blue, cobalt green, etc., and organic ones such as azo-based, naphthol-based, pyrazolone-based, anthraquinone-based, perylene-based, quinacridone-based, disazo-based, isoindolinone-based, benzimidazole-based, phthalocyanine-based, quinophthalone-based, etc. On the other hand, the black pigment is a pigment that exhibits black, and examples include inorganic ones such as iron black, iron-manganese composite oxide, iron-copper-manganese composite oxide, iron-chromium-cobalt composite oxide, copper-chromium composite oxide, copper-manganese-chromium composite oxide, etc., and other carbon black, etc. In addition, as the (B-2) component, for example, white pigments such as zinc oxide and aluminum oxide can also be used. These can be used singly or in combination of two or more.

[0037] In the present invention, as the component (B), an extender pigment (B-3) (hereinafter also referred to as the “(B-3) component”) can also be mixed. Examples of the (B-3) component include heavy calcium carbonate, precipitated calcium carbonate, kaolin, clay, pottery clay, china clay, diatomaceous earth, hydrated fine silica powder, talc, barite powder, barium sulfate, precipitated barium sulfate, barium carbonate, magnesium carbonate, silica powder, aluminum hydroxide, etc. These can be used singly or in combination of two or more. The (B-3) component can be used, for example, for the purposes of adjusting the solid content, adjusting the viscosity, adjusting the gloss (such as reducing the gloss), or improving the storage stability and pigment miscibility.

[0038] In the present invention, when based on 100 g of the solid content of component (A), the total oil absorption amount of component (B) (hereinafter also simply referred to as "total oil absorption amount") is 60 g or less, preferably 55 g or less. When the upper limit of the total oil absorption amount of component (B) is such a value, the curing of the resin component (A) by the organometallic compound (C) proceeds stably, lifting during overcoating is suppressed, the overcoating suitability becomes good, and a colored finish state with excellent aesthetic appearance can be obtained. The lower limit of the total oil absorption amount of component (B) is not particularly limited, but is preferably 3 g or more, more preferably 5 g or more. If the lower limit of the total oil absorption amount is such a value, it is suitable in terms of imparting viscosity, coating workability, finish properties, etc. The total oil absorption amount of component (B) can be set, for example, by adjusting the oil absorption amount, mixing ratio, etc. of each component (B) to be used.

[0039] In the present invention, the total oil absorption amount of component (B) is the amount (g) of boiled linseed oil absorbed by component (B) when based on 100 g of the solid content of component (A). Specifically, as component (B), when m types (m is an integer) represented by (B 1 ), (B 2 ), ··· (B m ) are used, the total oil absorption amount of component (B) is calculated by the following formula. Total oil absorption amount of component (B) = [{(Oil absorption amount of (B 1 ))} × {Number of grams of (B 1 ) when based on 100 g of the solid content of component (A)} / 100] + [{(Oil absorption amount of (B 2 ))} × {Number of grams of (B 2 ) when based on 100 g of the solid content of component (A)} / 100] + ··· [{(Oil absorption amount of (B m ))} × {Number of grams of (B m ) when based on 100 g of the solid content of component (A)} / 100]

[0040] The mixing ratio of component (B) in the coating agent of the present invention may be set within a range that satisfies the above range of total oil absorption. However, component (B-1) is preferably 5 to 150 parts by weight, more preferably 8 to 120 parts by weight, based on 100 parts by weight of the solid content of component (A). When component (B-2) is used, component (B-2) is preferably 0.1 to 100 parts by weight, more preferably 0.3 to 90 parts by weight, based on 100 parts by weight of the solid content of component (A). When component (B-3) is used, component (B-3) is preferably 50 parts by weight or less, more preferably 1 to 40 parts by weight, based on 100 parts by weight of the solid content of component (A).

[0041] The organometallic compound (C) (hereinafter also referred to as the "(C) component") is a component that acts as a curing catalyst or curing accelerator, etc. of the above (A) component. As the (C) component, for example, organometallic compounds containing metals such as cobalt, manganese, vanadium, cerium, iron, tin, zirconium, bismuth, aluminum, strontium, titanium, zinc, barium, copper, calcium, lead, nickel, etc. (for example, metal organic acid salt compounds, metal chelate compounds, metal alkoxide compounds, metal acylates, etc.) can be used. Specifically, as the (C) component, for example, cobalt octylate, cobalt naphthenate, manganese octylate, manganese naphthenate, iron octylate, iron naphthenate, tin octylate, tin naphthenate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctate, zirconium octylate, zirconium naphthenate, zirconium tetrakis(acetylacetonate), zirconium bis(butoxy)bis(acetylacetonate), zirconium ethoxide, zirconium n-propoxide, zirconium n-butoxide, aluminum monoacetylacetonate bis(ethyl acetoacetate), aluminum tris(acetylacetonate), aluminum ethyl acetoacetate diisopropylate, aluminum ethylate, aluminum isopropylate, aluminum sec-butyrate, titanium tetrakis(acetylacetonate), titanium bis(butoxy)bis(acetylacetonate), titanium ethoxide, titanium isopropoxide, titanium n-butoxide, zinc octylate, zinc naphthenate, barium octylate, barium naphthenate, copper octylate, copper naphthenate, calcium octylate, calcium naphthenate, etc. can be mentioned. These can be used alone or in combination of two or more.

[0042] In the present invention, as the component (C), an organometallic compound (C-1) containing at least one metal selected from the group consisting of cobalt, manganese, vanadium, cerium, and iron (hereinafter also referred to as the “(C-1) component”) and an organometallic compound (C-2) containing at least one metal selected from the group consisting of zirconium, bismuth, aluminum, strontium, titanium, zinc, barium, copper, and calcium (hereinafter also referred to as the “(C-2) component”) are preferably included. When such (C-1) component and (C-2) component are included, it is preferable in terms of improving effects such as curability, anti-lifting property, and suitability for overcoating. The weight ratio {(C-1):(C-2)} of the (C-1) component to the (C-2) component is preferably 1:99 to 50:50, more preferably 2:98 to 40:60 in terms of metal content conversion.

[0043] The mixing ratio of the component (C) is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 3 parts by weight in terms of metal content conversion with respect to 100 parts by weight of the solid content of the component (A). If the component (C) has such a mixing ratio, it is preferable in terms of curability, anti-lifting property, suitability for overcoating, etc.

[0044] The coating agent of the present invention is a so-called weak solvent type material containing an aliphatic hydrocarbon-containing non-aqueous solvent (D) (hereinafter also referred to as the “(D) component”) as a medium. Such a (D) component is a non-aqueous solvent that is less toxic than toluene, xylene, etc., has high work safety, and further has a small impact on air pollution. Examples of the aliphatic hydrocarbon include n-hexane, n-pentane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, etc. These can be used alone or in combination of two or more. In the present invention, an aliphatic hydrocarbon can also be introduced by using a mixed solvent such as mineral spirit. The aliphatic hydrocarbon is preferably contained in an amount of 5% by weight or more, more preferably 10 to 80% by weight based on the total amount of the (D) component.

[0045] (D) component may contain a solvent miscible with aliphatic hydrocarbons. Such solvents include, for example, petroleum solvents such as petroleum ether, petroleum naphtha, and solvent naphtha, as well as ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, etc. Preferred solvents include, for example, petroleum solvents (aromatic hydrocarbon-containing petroleum mixed solvents) having a mixed aniline point or aniline point of 12 to 70 °C. The mixed aniline point or aniline point is a value measured by the method of JIS K2256:2013.

[0046] (D) component's mixing ratio is preferably 100 to 300 parts by weight, more preferably 120 to 250 parts by weight, based on 100 parts by weight of the solid content of (A) component, from the viewpoints of workability and finish during overcoating. Note that the solvent used as the medium for each component is also included in (D) component.

[0047] In addition to the above-mentioned components, the coating agent of the present invention may contain various components to the extent that it does not affect the effects of the present invention. Such components include, for example, plasticizers, preservatives, fungicides, algicides, defoamers, leveling agents, pigment dispersants, thickeners, anti-skinning agents, dehydrating agents, matting agents, ultraviolet absorbers, light stabilizers, antioxidants, catalysts, etc. It may also contain a resin component other than the above (A) component. The coating agent of the present invention can be produced by uniformly stirring and mixing the above (A) to (D) components and, if necessary, such various components by a conventional method.

[0048] The coating agent of the present invention can be mainly applied to buildings, civil engineering structures, etc. Examples of the base material constituting such a part include concrete, mortar, siding board, extruded board, gypsum board, perlite board, wooden board, plastic board, metal board, etc. These base materials may be those subjected to some surface treatment (such as filler treatment, putty treatment, surfacer treatment, sealer treatment, etc.), or those on which a coating film has already been formed. The coating agent of the present invention is particularly suitable for outdoor use, such as under conditions where titanium oxide is likely to generate radicals, for example, when exposed to sunlight. Further, it is desirable to use the coating agent of the present invention in a one-component form.

[0049] The coating agent of the present invention can be diluted during painting. As the diluent, the above component (D) is preferable, and it is desirable to dilute within the range where the total amount of component (D) after dilution satisfies the above mixing ratio.

[0050] As the painting method, various methods such as brush painting, roller painting, spray painting, etc. can be adopted. The coating amount during painting is preferably 30 - 250 g / m 2 , more preferably 50 - 200 g / m 2 per application. In the present invention, once painting is performed, after the coating film is dried, the next painting (overcoating) can be carried out. The drying temperature is preferably -10 to 50 °C, more preferably -5 to 40 °C. The number of painting times is preferably 2 or more.

Examples

[0051] Examples and comparative examples are shown below to clarify the features of the present invention more clearly.

[0052] (Manufacture of coating agent) Each component was uniformly mixed by a conventional method at the weight ratios shown in Tables 1 - 3 to manufacture each coating agent. The components used are as follows.

[0053] · Resin 1: An acid group-containing non-aqueous dispersion resin with an oxidatively polymerizable group (resin component: a soybean oil fatty acid-modified product of an epoxy group-containing acrylic styrene resin, a non-aqueous dispersion resin using mineral spirit as a medium, unsaturated fatty acid composition ratio: 10% by weight, weight average molecular weight: 130,000, acid value: 2 mg KOH / g, solid content: 50% by weight) · Resin 2: An acid group-containing non-aqueous dispersion resin with an oxidatively polymerizable group (resin component: a soybean oil fatty acid-modified product of an epoxy group-containing acrylic styrene resin, a non-aqueous dispersion resin using mineral spirit as a medium, unsaturated fatty acid composition ratio: 10% by weight, weight average molecular weight: 130,000, acid value: 0.2 mg KOH / g, solid content: 50% by weight) · Resin 3: A non-aqueous dispersion resin containing an oxidatively polymerizable group (resin component: a soybean oil fatty acid-modified product of an epoxy group-containing acrylic styrene resin, a non-aqueous dispersion resin using mineral spirit as a medium, unsaturated fatty acid composition ratio: 10% by weight, weight average molecular weight: 130,000, acid value: 0 mg KOH / g, solid content: 50% by weight) · Resin 4: A soluble resin containing an acid group (resin component: an acrylic styrene resin, a soluble resin using mineral spirit as a medium, weight average molecular weight: 11,000, acid value: 2 mg KOH / g, amine value: 1 mg KOH / g, hydroxyl value: 30 mg KOH / g, solid content: 50% by weight) · Resin 5: A soluble resin containing an oxidatively polymerizable group and an acid group (resin component: a soybean oil fatty acid-modified product of an epoxy group-containing acrylic styrene resin, a soluble resin using mineral spirit as a medium, unsaturated fatty acid composition ratio: 18% by weight, weight average molecular weight: 11,000, acid value: 1 mg KOH / g, hydroxyl value: 40 mg KOH / g, solid content: 50% by weight) · Resin 6: A soluble resin containing an oxidatively polymerizable group and an acid group (resin component: a soybean oil fatty acid-modified product of an epoxy group-containing acrylic styrene resin, a soluble resin using mineral spirit as a medium, unsaturated fatty acid composition ratio: 18% by weight, weight average molecular weight: 80,000, acid value: 1 mg KOH / g, hydroxyl value: 40 mg KOH / g, solid content: 50% by weight) · Resin 7: Oxidation-polymerizable group· Acid group-containing soluble resin (resin component: soybean oil fatty acid-modified product of epoxy group-containing acrylic styrene resin, soluble resin using mineral spirit as the medium, unsaturated fatty acid composition ratio: 18% by weight, weight average molecular weight: 120,000, acid value: 1 mg KOH / g, hydroxyl value: 40 mg KOH / g, solid content: 50% by weight) · Resin 8: Oxidation-polymerizable group· Acid group-containing soluble resin (resin component: soybean oil fatty acid-modified product of epoxy group-containing acrylic styrene resin, soluble resin using mineral spirit as the medium, unsaturated fatty acid composition ratio: 18% by weight, weight average molecular weight: 120,000, acid value: 1 mg KOH / g, hydroxyl value: 16 mg KOH / g, solid content: 50% by weight) · Resin 9: Oxidation-polymerizable group· Acid group-containing soluble resin (resin component: soybean oil fatty acid-modified product of epoxy group-containing acrylic styrene resin, soluble resin using mineral spirit as the medium, unsaturated fatty acid composition ratio: 18% by weight, weight average molecular weight: 120,000, acid value: 1 mg KOH / g, hydroxyl value: 8 mg KOH / g, solid content: 50% by weight) · Resin 10: Oxidation-polymerizable group· Acid group-containing soluble resin (resin component: soybean oil fatty acid-modified product of epoxy group-containing acrylic styrene resin, soluble resin using mineral spirit as the medium, unsaturated fatty acid composition ratio: 18% by weight, weight average molecular weight: 120,000, acid value: 1 mg KOH / g, hydroxyl value: 2 mg KOH / g, solid content: 50% by weight) · Titanium Oxide 1: Surface-treated rutile-type titanium oxide (oil absorption: 24 g / 100 g, TiO 2 content: 93%, surface treatment compounds: silica, alumina, zirconia) · Titanium Oxide 2: Surface-treated rutile-type titanium oxide (oil absorption: 22 g / 100 g, TiO 2 content: 87%, surface treatment compounds: silica, alumina, zirconia, organic compound) · Titanium Oxide 3: Surface-treated rutile-type titanium oxide (oil absorption: 33 g / 100 g, TiO 2 content: 88%, surface treatment compounds: silica, alumina) · Titanium Oxide 4: Untreated rutile-type titanium oxide (oil absorption: 17 g / 100 g, TiO 2 content: 99%) · Titanium Oxide 5: Anatase-type Titanium Oxide (Oil Absorption: 23 g / 100 g, TiO 2 Content: 99%) · Color Pigment 1: Black Pigment (Carbon Black, Oil Absorption: 98 g / 100 g) · Color Pigment 2: Yellow Pigment (Hydrated Ferric Oxide, Oil Absorption: 30 g / 100 g) · Color Pigment 3: Red Pigment (Ferric Oxide, Oil Absorption: 25 g / 100 g) · Color Pigment 4: Blue Pigment (Copper Phthalocyanine Blue, Oil Absorption: 35 g / 100 g) · Filler 1: Filler (Hydrous Micropowdered Silica, Oil Absorption: 250 g / 100 g) · Organometallic Compound 1: Mineral Spirit Solution of Cobalt Naphthenate · Organometallic Compound 2: Mineral Spirit Solution of Zirconium Naphthenate · Organometallic Compound 3: Mineral Spirit Solution of Barium Naphthenate · Organometallic Compound 4: Aluminum Monoacetylacetonate Bis(Ethyl Acetoacetate) · Dispersant: Urethane-based Dispersant · Thickener: Amide Wax-based Thickener · Antifoaming Agent: Mineral Oil-based Antifoaming Agent · Solvent: Non-aqueous Solvent Containing Aliphatic Hydrocarbons (Mixture of Mineral Spirit and Petroleum Mixed Solvent Containing Aromatic Hydrocarbons, Aliphatic Hydrocarbon Content Ratio: 65 wt%)

[0054] ○ Test I For each coating agent, the following tests were carried out.

[0055] · Overcoating Suitability 1 On a slate board pre-coated with an epoxy resin undercoat, the coating agent was spray-coated at an application rate of 100 g / m 2 . Indoors under sunlight during the day, after drying and curing for a predetermined time (48 hours, 72 hours), using a brush, the same coating agent was applied at an application rate of 100 g / m 2Partial overcoating was performed. At this time, the surface state of the coating film was observed, and those without lifting phenomenon were rated as "a", those with very slight lifting phenomenon were rated as "b", those with slight lifting phenomenon were rated as "c", and those with obvious lifting phenomenon were rated as "d". Evaluation was carried out in four levels (a > b > c > d, practical level is a - c). The results are shown in Tables 1 - 3.

[0056] · Overcoating suitability 2 On a slate board pre-coated with an epoxy resin undercoat, a coating agent was spray-coated at an application rate of 100 g / m 2 . After drying and curing for 48 hours indoors under sunlight during the day, using a brush, the same coating agent was partially overcoated at an application rate of 100 g / m 2 . After leaving this specimen for 48 hours, the color difference (△E) between the spray-coated area and the brush-coated area was measured with a color difference meter. The evaluation criteria were as follows: those with △E less than 0.5 were rated as "a", those with △E of 0.5 or more and less than 1.0 were rated as "b", those with △E of 1.0 or more and less than 1.5 were rated as "c", and those with △E of 1.5 or more were rated as "d" (practical level is a - c). The results are shown in Tables 1 - 3. For Comparative Examples 2 - 5, since the results were inferior to those of the above overcoating suitability 1, no evaluation was carried out.

[0057] (Test results) In Examples 1 - 21 (especially Examples 2 - 9, 14 - 21), good results were obtained in overcoating suitability 1 and 2. Also, the hiding power was good.

[0058] [Table 1]

[0059] [Table 2]

[0060] [Table 3]

[0061] ○Test II For the coating agents of Examples 5 and 14 to 21, the following tests were carried out.

[0062] ·Finish (specular gloss) On one side of a glass plate, the coating agent was applied using a film applicator with a gap of 125 μm, and the specular gloss (measurement angles 60 degrees and 20 degrees) when the coated surface was placed horizontally and dried in the standard state for 48 hours was measured. The evaluation was carried out as follows: When the 60-degree specular gloss is 85 or more and the 20-degree specular gloss is 75 or more, it is rated as "a". When the 60-degree specular gloss is 85 or more and the 20-degree specular gloss is less than 75, it is rated as "b". When the 60-degree specular gloss is 80 or more and less than 85, it is rated as "c". When the 60-degree specular gloss is less than 80, it is rated as "d". This was done. The results are shown in Table 4.

[0063] ·Durability On a slate plate pre-coated with an epoxy resin undercoat, the coating agent was spray-coated at an application rate of 100 g / m 2 and after 2 hours, the same coating agent was spray-coated again at an application rate of 100 g / m 2 and cured for 3 days in the standard state (at a temperature of 23°C and a relative humidity of 50% environment). For the test specimens prepared by the above method, a total of 10 cycles of a temperature and humidity cycling test with water immersion for 18 hours, leaving at -20°C for 3 hours, and leaving at 50°C for 3 hours as one cycle were carried out, and then the appearance of the coating film was confirmed, and the occurrence state of defects (swelling, peeling, cracking, etc.) was evaluated. The evaluation was carried out in four grades (a > b > c > d, and the practical level is a to c), where "a" is for those without the occurrence of defects and "d" is for those with obvious occurrence of defects. The results are shown in Table 4.

[0064] (Test results) In Examples 15 to 21, good results were also obtained in terms of finish and durability.

[0065] [Table 4]

Claims

【Claim 1】 A coating agent comprising a resin component (A), a pigment (B), an organometallic compound (C), and an aliphatic hydrocarbon-containing non-aqueous solvent (D), wherein the resin component (A) includes a non-aqueous dispersion resin (A-1) and a soluble resin (A-2), the non-aqueous dispersion resin (A-1) and / or the soluble resin (A-2) has an oxidation polymerizable group, the non-aqueous dispersion resin (A-1) and the soluble resin (A-2) have an acid value, the acid value is 0.3 to 30 mgKOH / g, the pigment (B) includes a surface-treated rutile-type titanium oxide (B-1), when based on 100 g of the solid content of the resin component (A), the total oil absorption amount of the pigment (B) is 60 g or less, and the surface-treated rutile-type titanium oxide (B-1) has an oil absorption amount of 30 g / 100 g or less and a TiO₂ content of 80 to 89%, the organometallic compound (C) includes an organometallic compound (C-1) containing one or more metals selected from the group consisting of cobalt, manganese, vanadium, cerium, and iron, and an organometallic compound (C-2) containing one or more metals selected from the group consisting of zirconium, bismuth, aluminum, strontium, titanium, zinc, barium, copper, and calcium, and the weight ratio {(C-1):(C-2)} of the component (C-1) to the component (C-2) is 1:99 to 50:50 in terms of metal conversion, a coating agent characterized by the above.

Images