JP2023104036A - covering material - Google Patents

Abstract

To provide a covering material having excellent adhesion to various base and top coating materials.SOLUTION: A covering material is composed of a resin component (A), an aliphatic hydrocarbon-containing nonaqueous solvent (B), a polyisocyanate compound (C), and an organic amine compound (D). The resin component (A) includes a non-water-dispersible resin (A-1) and a soluble resin (A-2). The non-water-dispersible resin (A-1) and/or the soluble resin (A-2) has a hydroxy group.SELECTED DRAWING: None

Description

The present invention relates to novel dressings.

Conventionally, inorganic base materials such as concrete, mortar, slate boards, calcium silicate boards, and siding boards have been widely used as base materials constituting buildings, civil engineering structures, and the like. When these surfaces are coated, they are usually coated with a primer in order to ensure adhesion and to prevent swelling, peeling, lifting, etc. of the coating over time. In addition, when repairing an old coating film surface, especially when repairing a coating film having functionality such as high weather resistance and stain resistance provided in exterior building materials, a primer is similarly required. For this reason, there is a demand for an undercoat material that has good adhesion to various substrates and substrates such as coating films.

Such undercoat materials are mainly classified into solvent-based undercoat materials and water-based undercoat materials, but solvent-based undercoat materials are often used in terms of adhesion. Among them, in recent years, in consideration of safety during painting, work hygiene, etc., or environmental problems, for example, a weak solvent type undercoat material that uses an aliphatic hydrocarbon solvent as a main solvent such as Patent Document 1 has been used. Used a lot.

JP 2020-066744 A

On the other hand, as described above, in consideration of environmental issues, etc., weak solvent-type top coating materials and water-based top coating materials are often used as top coating materials. However, depending on the coating conditions of the weak solvent type undercoat material and topcoat material, it may be difficult to ensure sufficient adhesion, and there is room for improvement.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a coating material which has excellent adhesion and which can be suitably used as a weak solvent type undercoat material.

In order to solve such problems, the present inventors, as a result of intensive studies, have conceived of a coating material that uses a non-aqueous dispersion type resin and a soluble type resin together as a resin component and further contains a specific compound as an essential component. As a result, the present invention has been completed.

That is, the present invention has the following features.
1. Constituent components include a resin component (A), an aliphatic hydrocarbon-containing non-aqueous solvent (B), a polyisocyanate compound (C), and an organic amine compound (D),
The resin component (A) includes a non-aqueous dispersion resin (A-1) and a soluble resin (A-2),
A coating material, wherein the non-aqueous-dispersible resin (A-1) and/or the soluble resin (A-2) have a hydroxyl group.
2. As a component, it contains an extender pigment,
1. The resin component (A) contains 50 to 600 parts by weight of the extender pigment with respect to 100 parts by weight of the solid content of the resin component (A). The covering material described in .
3. The solid content weight ratio [(A-1)/(A-2)] between the non-aqueous dispersion type resin (A-1) and the soluble resin (A-2) is 2/98 to 80/20. 1. or 2. The covering material described in .

The coating material of the present invention can exhibit excellent performance in terms of adhesion.

EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention is demonstrated.

The coating material of the present invention contains, as constituent components, a resin component (A), an aliphatic hydrocarbon-containing non-aqueous solvent (B), a polyisocyanate compound (C) and an organic amine compound (D).

The coating material of the present invention contains a non-aqueous-dispersible resin (A-1) and a soluble resin (A-2) as the resin component (A) (hereinafter also referred to as "(A) component"). Characterized by In the present invention, the combined use of the non-aqueous-dispersible resin (A-1) and the soluble resin (A-2) contributes to improved adhesion and the like.

The non-aqueous-dispersible resin (A-1) (hereinafter also referred to as "(A-1) component") is a resin that can be dispersed in the aliphatic hydrocarbon-containing non-aqueous solvent (B). Specifically, it has both a resin portion that is soluble in the aliphatic hydrocarbon-containing non-aqueous solvent (B) and a resin portion that is not soluble, and is dispersed in the non-aqueous solvent (B) in the form of resin particles. It is what we are doing. Component (A-1) can be obtained, for example, by polymerizing various vinyl-based monomers in the presence of a resin soluble in the non-aqueous solvent (B). The weight average molecular weight of component (A-1) is preferably 10,000 to 500,000 (more preferably 20,000 to 300,000). The glass transition temperature of component (A-1) is preferably -5°C to 70°C (more preferably 10°C to 60°C). The glass transition temperature is a value determined by Fox's formula based on the vinyl monomer that constitutes the resin. In the present invention, "a to b" is synonymous with "a or more and b or less".

The soluble resin (A-2) is a resin that can be dissolved in the aliphatic hydrocarbon-containing non-aqueous solvent (B). Component (A-2) can be obtained, for example, by polymerizing various vinyl monomers in the above non-aqueous solvent (B) in a conventional manner. The weight average molecular weight of component (A-2) is preferably 2,000 to 300,000 (more preferably 10, 000 to 250,000, more preferably 30,000 to 220,000, particularly preferably 50,000 to 200,000). The glass transition temperature of component (A-2) is preferably -5°C to 70°C (more preferably 10°C to 60°C).

The solid content weight ratio of component (A-1) and component (A-2) [(A-1) component/(A-2) component] is preferably 2/98 to 80/20 (more preferably 3/ 97 to 60/40, more preferably 4/96 to 45/55, particularly preferably 5/95 to 40/60). Within such a range, the effects of the present invention can be enhanced. In particular, it is advantageous in adhesion under a low temperature environment.

In the component (A) of the present invention, among the components (A-1) and (A-2), at least the component (A-1) has an oxidatively polymerizable group (is an oxidatively polymerizable resin). Preferably, both the (A-1) component and the (A-2) component have oxidatively polymerizable groups. As a result, the component (A) is air-oxidized by the oxidatively polymerizable double bond (oxidatively polymerizable group) and cured and dried. Thereby, curability can be improved and adhesion can be improved. In order to provide the component (A-1) and/or the component (A-2) with oxidatively polymerizable groups, for example, the following resins may be used.

1) A resin obtained by copolymerizing a vinyl monomer having an oxidatively polymerizable group with another vinyl monomer copolymerizable with this monomer.
2) After copolymerizing an epoxy group-containing vinyl monomer with another vinyl monomer copolymerizable with this monomer, unsaturated fatty acid is added to the epoxy group-containing vinyl monomer. Obtained resin.
3) A resin obtained by copolymerizing and/or graft-polymerizing a vinyl monomer having an oxidatively polymerizable group and/or another vinyl monomer copolymerizable with this monomer onto an alkyd resin.

Examples of vinyl monomers having an oxidatively polymerizable group in 1) and 3) above include vinyl monomers obtained by adding unsaturated fatty acids to epoxy group-containing vinyl monomers. This vinyl monomer is obtained by reacting an epoxy group with a carboxyl group in an unsaturated fatty acid. The resin of 2) above is obtained by an addition reaction of an unsaturated fatty acid to an epoxy group in the resin. A catalyst such as a tertiary amine or a quaternary ammonium salt can be used when the epoxy group and the unsaturated fatty acid are reacted.

Specific examples of epoxy group-containing vinyl monomers include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 3,4-oxycyclohexylpropyl (meth)acrylate, and allyl glycidyl ether. These can be used singly or in combination of two or more.

Examples of unsaturated fatty acids 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, perilla oil fatty acid, safflower oil fatty acid, hemp seed oil fatty acid, and grape kernel oil. fatty acids, tall oil fatty acids, sunflower oil fatty acids, cottonseed oil fatty acids, corn oil fatty acids, walnut oil fatty acids and the like. These can be used singly or in combination of two or more. The composition ratio of the unsaturated fatty acids in the component (A-1) and the component (A-2) is determined from the viewpoint of adhesion and various coating properties, the resin solid content of the component (A-1) or the component (A-2) is preferably 0.1 to 40% by weight, more preferably 0.2 to 35% by weight.

Examples of the vinyl monomer having an oxidatively polymerizable group in 1) and 3) include dicyclopentadieneoxyalkyl group-containing vinyl monomers such as dicyclopentadieneoxyalkyl (meth)acrylate, and allyl (meth)acrylate. Allyl group-containing vinyl monomers such as can also be used. These can be used singly or in combination of two or more.

As the alkyd resin in 3) above, polycondensation of a polyhydric alcohol and a polycarboxylic acid and modification with a drying oil, an unsaturated fatty acid or the like can be used. Examples of polyhydric alcohols include ethylene glycol, glycerin, and pentaerythritol, and examples of polyvalent carboxylic acids include phthalic anhydride and maleic anhydride. Drying oils include, for example, linseed oil, tung oil, hollyhock oil, safflower oil, and the like. The alkyd resin modification rate in component (A-1) and component (A-2) is based on the resin solid content of component (A-1) or component (A-2) from the viewpoint of adhesion and various coating properties. , preferably 0.1 to 40% by weight, more preferably 0.2 to 35% by weight.

Examples of other vinyl monomers in 1) to 3) above include (meth)acrylic acid alkyl esters and aromatic monomers. Among these, specific examples of (meth)acrylic acid alkyl esters 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 aromatic monomers include styrene, 2-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, vinylanisole, vinylnaphthalene, and divinylbenzene. These can be used singly or in combination of two or more. Examples of such vinyl monomers that can be used include carboxyl group-containing vinyl monomers, amino group-containing vinyl monomers, and hydroxyl group-containing vinyl monomers. Component (A) includes, as other monomers, copolymers of at least (meth)acrylic acid alkyl esters, copolymers of (meth)acrylic acid alkyl esters and aromatic monomers, and the like. preferred.

The present invention is characterized in that the component (A-1) and/or the component (A-2) have a hydroxyl value. This can enhance the effect of the present invention. The hydroxyl value of component (A-1) and/or component (A-2) is preferably 1 to 150 mgKOH/g (more than preferably 5 to 100 mgKOH/g, more preferably 10 to 80 mgKOH/g). Within such a range, curability (initial drying property) is enhanced, and adhesion can be further enhanced. In the present invention, at least component (A-1) preferably has the above hydroxyl value. The hydroxyl value is a value represented by the number of mg of potassium hydroxide that is equimolar to the hydroxyl group contained in 1 g of the resin solid content.

In order to set the hydroxyl value in component (A) within the above range, other vinyl monomers in 1) to 3) may be, for example, hydroxyl-containing vinyl monomers. Examples of the hydroxyl group-containing vinyl monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxy(meth)acrylate. Examples include hydroxyalkyl (meth)acrylates such as butyl and 4-hydroxybutyl (meth)acrylate. These can be used singly or in combination of two or more.

In addition, it is preferred that component (A-1) and/or component (A-2) have an acid value. This can enhance the effect of the present invention. The acid value of the resin component is preferably 0.1 to 30 mgKOH/g (more preferably 0.3 to 20 mgKOH/g) based on the resin solid content of component (A-1) or component (A-2). be. Within such a range, curability (initial drying property) is enhanced, and adhesion can be further enhanced. In the present invention, both the (A-1) component and the (A-2) component desirably have the above acid values. The acid value is a value represented by the number of mg of potassium hydroxide that is equimolar with the acid groups contained in 1 g of the resin solid content.

In order to set the acid value in component (A) within the above range, for example, a carboxyl group-containing vinyl monomer may be used as the other vinyl monomer in 1) to 3) above. Carboxyl group-containing vinyl monomers include, for example, 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-poly butyrolactone mono(meth)acrylate, ω-carboxy-polyvalerolactone mono(meth)acrylate, ω-carboxy-polycaprolactone mono(meth)acrylate, ω-carboxy-polycaprylolactone mono(meth)acrylate, ω-carboxy- Polylauryrolactone 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 singly or in combination of two or more.

Furthermore, it is preferred that component (A-1) and/or component (A-2) have an amine value. The amine value in component (A-1) and/or component (A-2) is preferably 0.1 mg KOH/g or more ( More preferably 0.3 to 10 mgKOH/g).

In order to set the amine value in component (A) within the above range, other vinyl monomers in 1) to 3) above may be, for example, amino group-containing vinyl monomers, hydroxyl group-containing vinyl monomers, etc. should be used. Examples of the amino group-containing vinyl monomer include N-methylaminoethyl (noethyl (meth)acrylate, dimethylaminoethyl vinyl ether, N-(2-dimethylaminoethyl) acrylamide, N-(2-dimethylaminoethyl) and methacrylamide, etc. These can be used singly or in combination of two or more.

The above aliphatic hydrocarbon-containing non-aqueous solvent (B) (hereinafter also referred to as "(B) component") is less toxic than toluene, xylene, etc., has high safety in work, and has an effect on air pollution. is a small non-aqueous solvent. Examples of aliphatic hydrocarbons include n-hexane, n-pentane, n-octane, n-nonane, n-decane, n-undecane and n-dodecane. These can be used singly or in combination of two or more. In the present invention, aliphatic hydrocarbons can also be introduced by using mixed solvents such as mineral spirits. Aliphatic hydrocarbons are preferably contained in an amount of 5% by weight or more (more preferably 10 to 80% by weight) relative to the total amount of component (B).

The component (B) may contain a solvent miscible with aliphatic hydrocarbons. Examples of such solvents include petroleum solvents such as petroleum ether, petroleum naphtha and solvent naphtha, as well as ethyl acetate, butyl acetate, methyl ethyl ketone and methyl isobutyl ketone. petroleum-based solvents (aromatic hydrocarbon-containing petroleum mixed solvents) having a 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.

The mixing ratio of component (B) is preferably 100 to 500 parts by weight, more preferably 120 to 400 parts by weight, per 100 parts by weight of the solid content of component (A). The component (B) also includes a solvent used as a medium for each component.

The polyisocyanate compound (C) (hereinafter also referred to as "component (C)") has two or more isocyanate groups in one molecule and reacts with the hydroxyl groups of component (A). As the component (C), those capable of reacting with the component (C) at room temperature are suitable. The room temperature referred to here is preferably −10° C. or higher and 50° C. or lower, more preferably 5° C. or higher and 40° C. or lower.

Component (C) includes at least one type of diisocyanate selected from aliphatic diisocyanates and alicyclic diisocyanates, an alcohol component, and optionally a polyol component or the like that is pre-alphanate-formed, biuret-formed, dimerized (uretidione-formed), 3 Derivatization by quantification (isocyanurate formation), adduct formation, carbodiimidation reaction, etc., and mixtures thereof can be mentioned. These can be used singly or in combination of two or more.

Aliphatic diisocyanate is a compound having a saturated aliphatic group in the molecule, such as 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane methylene diisocyanate (HDI)), 1,6-diisocyanato-2,2,4-trimethylhexane, methyl 2,6-diisocyanatohexanoate (lysine diisocyanate), and the like. On the other hand, alicyclic diisocyanates are compounds having a cyclic aliphatic group in the molecule, and examples thereof include 5-isocyanato-1-isocyanatomethyl-1,3,3-trimethylcyclohexane (isophorone diisocyanate), 1,3 -bis(isocyanatomethyl)cyclohexane (hydrogenated xylylene diisocyanate), bis(4-isocyanatocyclohexyl)methane (hydrogenated diphenylmethane diisocyanate), 1,4-diisocyanatocyclohexane and the like. Among these, HDI is most preferable because of its excellent weather resistance and flexibility.

Examples of alcohol components include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, 1-pentanol, 2-pentanol, isoamyl alcohol, 1-hexanol, and 2-hexanol. , 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, 3,3,5-trimethyl-1-hexanol, tridecanol, pentadecanol, palmityl alcohol, stearyl alcohol, cyclopentanol, cyclohexanol, methyl cyclohexanol, trimethylcyclohexanol and the like. These can be used alone or in combination of two or more.

Examples of polyol components include polyether polyols, polyester polyols, and polyolefin polyols. Polyether polyols such as polypropylene triol, polypropylene glycol, and polytetramethylene glycol are particularly preferred in the present invention. These can be used alone or in combination of two or more.

The amount of component (C) is preferably 0.01 to 0.5 (more preferably 0 .05 to 0.3). Within such a range, excellent storage stability and sufficient adhesion can be obtained. In particular, excellent effects can be exhibited in terms of adhesion to the base.

Furthermore, as component (C), it is preferable to include a polyisocyanate compound having an isocyanate group content of 10 wt% or more (more preferably 15 wt% or more and 30 wt% or less) in the solid content. As a result, sufficient adhesion can be obtained, and water resistance is enhanced, which is effective in suppressing blistering of the coating. In the present invention, the isocyanate group content is defined as the content (% by weight) of isocyanate groups contained in the solid content of the polyisocyanate compound. Value determined by back titration.

The organic amine compound (D) (hereinafter also referred to as "(D) component") is a component that acts as an adhesion improver to the base material and topcoat material. In the coating material containing the component (A-1) of the present invention, the component (A-2), the component (B), and the component (C), by including the component (D), for the base material and the topcoat material Stable adhesion can be obtained, and in particular, it is effective in improving adhesion to the topcoat material, and even when the topcoat material is an aqueous coating material, excellent adhesion can be exhibited.

Component (D) includes, for example, urea compounds such as urea, thiourea, methylurea, ethylurea, dimethylurea, diethylurea, ethyleneurea, guanylurea, guanylthiourea, azodicarbonamide, glycolylurea, and acetylurea; hydrazine, isopropylhydrazine, butylhydrazine, benzylhydrazine, phenylhydrazine, hydrabenzene, methylcarbazate, propionic hydrazide, carbohydrazide, adipic dihydrazide, dodecanediohydrazide, thiocarbohydrazide, isophthalic dihydrazide, 4,4'- hydrazides such as oxybisbenzenesulfonylhydrazine; pyrrolidine, piperidine, morpholine, dicyandiamide and the like. These can be used singly or in combination of two or more. Thereby, the effects of the present invention can be enhanced without inhibiting the curing of the component (A).

In the present invention, it is preferable that the component (D) contains a urea compound (especially ethylene urea). As a result, stable adhesion to the base material and topcoat material is obtained, and in particular, it is effective in improving adhesion to the topcoat material, and even when the topcoat material is an aqueous coating material, the adhesion is even better. effect can be exhibited.

Furthermore, it is preferable to use the component (D) of the present invention by dissolving it in a solvent. The solvent is not particularly limited and any known polar solvent can be used as long as it can dissolve the component (D). In the present invention, alcoholic solvents such as ethanol and methanol are suitable. This makes it possible to uniformly disperse the component (D) in the coating material, thereby enhancing the effects of the present invention.

The amount of component (D) to be blended is preferably 0.05 to 10 parts by weight (more preferably 0.1 to 5 parts by weight) per 100 parts by weight of the solid content of component (A). With such a range,
Sufficient adhesion can be obtained. In particular, excellent effects can be exhibited in terms of adhesion to topcoat materials.

The coating material of the present invention preferably contains a coloring pigment (E) and/or an extender pigment (F) in addition to the above components.

As the coloring pigment (E) (hereinafter also referred to as "component (E)"), chromatic pigments, white pigments, black pigments, and the like can be used. Among these, chromatic pigments are pigments exhibiting chromatic colors such as yellow, orange, red, green, blue, and purple, for example. Examples of such chromatic pigments include inorganic pigments such as ferric oxide, hydrated ferric oxide, ultramarine blue, cobalt blue and cobalt green; azo-based, naphthol-based, pyrazolone-based, anthraquinone-based, perylene-based, Examples include quinacridone-based, disazo-based, isoindolinone-based, benzimidazole-based, phthalocyanine-based, and quinophthalone-based organic materials. On the other hand, white pigments are pigments that exhibit white color, and examples thereof include titanium oxide, zinc oxide, and aluminum oxide. Black pigments are pigments exhibiting black color, for example, iron black, iron-manganese composite oxide, iron-copper-manganese composite oxide, iron-chromium-cobalt composite oxide, copper-chromium composite oxide, copper- Inorganic materials such as manganese-chromium composite oxides, carbon black, and the like are included. These can be used singly or in combination of two or more. Moreover, the surface thereof may be subjected to some kind of treatment. The average particle size of component (E) is preferably 1 μm or less, more preferably 0.01 to 0.9 μm.

The amount of component (E) to be blended is preferably 5 to 100 parts by weight (more preferably 10 to 80 parts by weight) per 100 parts by weight of the solid content of component (A). If the component (E) is in such a ratio, the coating material can be colored in a desired color, and the concealability, beauty and the like can be enhanced.

The extender (F) (hereinafter also referred to as "component (F)"), for example, homogenizes the substrate surface and contributes to adhesion to the substrate and topcoat material. Specifically, roughening and cracking of the surface of the base material due to deterioration are repaired, the surface is flattened, and the overall color tone is adjusted to homogenize the appearance. Furthermore, the occurrence of problems such as blisters, cracks, and peeling in the topcoat material can be suppressed due to the anchoring effect of fine unevenness derived from the component (F). Although the reason why such an effect is exhibited is not clear, the component (F) increases the solid content ratio of the coating material, imparts an appropriate viscosity, and improves the coating strength, etc., and this is effectively acting. It is assumed that

Component (F) includes, for example, heavy calcium carbonate, trace calcium carbonate, kaolin, clay, china clay, china clay, diatomaceous earth, hydrated finely divided silicic acid, talc, barite powder, barium sulfate, precipitated barium sulfate, barium carbonate, Examples include magnesium carbonate, silica powder, and aluminum hydroxide. These can be used singly or in combination of two or more. The average particle size of component (F) is preferably 0.1 to 100 μm (preferably 1 to 80 μm).

The amount of component (F) is preferably 50 to 600 parts by weight (more preferably 60 to 500 parts by weight, still more preferably 100 to 450 parts by weight) per 100 parts by weight of the solid content of component (A). be. When it is within such a range, the above effects can be sufficiently exhibited, and sufficient adhesion to the base material and topcoat material (especially topcoat material) can be obtained.

In the present invention, the above component (E) and / or the above component (F), the pigment volume concentration (PVC) (hereinafter also referred to as "PVC") in the formed coating film is preferably 30 to 80% (more preferably 35% ~65%). With such a pigment volume concentration (PVC), a coating film having sufficient adhesion can be formed.

In the coating material of the present invention, in addition to the above components, the organometallic compound (G) (hereinafter also referred to as "(G) component") acts as a curing catalyst or curing accelerator for the above component (A). is an ingredient. Component (G) includes, for example, organometallic compounds containing metals such as cobalt, manganese, vanadium, cerium, iron, tin, zirconium, bismuth, aluminum, strontium, titanium, zinc, barium, copper, calcium, lead, and nickel. (For example, metal organic acid salt compounds, metal chelate compounds, metal alkoxide compounds, metal acylate compounds, etc.) and the like can be used. Specific examples of component (G) include cobalt octylate, cobalt naphthenate, manganese octylate, manganese naphthenate, iron octylate, iron naphthenate, tin octylate, tin naphthenate, dibutyltin diacetate, and dibutyltin dilaurate. , dibutyltin dioctiate, zirconium octoate, zirconium naphthenate, zirconium tetrakis (acetylacetonate), zirconium bis (butoxy) bis (acetylacetonate), zirconium ethoxide, zirconium n-propoxide, zirconium n-butoxide, aluminum monoacetylacetonate bis(ethylacetoacetate), aluminum tris(acetylacetonate), aluminum ethylacetoacetate diisopropylate, aluminum ethylate, aluminum isopropylate, aluminum sec-butylate, 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, octylic acid calcium, calcium naphthenate, and the like. These can be used singly or in combination of two or more.

The amount of component (G) to be blended is preferably 0.1 to 15 parts by weight (more preferably 0.3 to 10 parts by weight, more preferably 0.3 to 10 parts by weight, more preferably 0.1 to 15 parts by weight) per 100 parts by weight of the solid content of component (A). 5 to 8 parts by weight). Also, the amount of metal in component (G) is preferably 0.01 to 5 parts by weight (more preferably 0.05 to 3 parts by weight) relative to 100 parts by weight of the solid content of component (A). be. By being in such a range, the curability (initial drying property) can be enhanced, and sufficient adhesion can be obtained with respect to the base material and the topcoat material.

The coating material of the present invention may further contain a curing accelerator (X) that enhances the activity of the component (G). Examples of curing accelerators include 1,10-phenanthroline and 2,2'-dipyridyl. These can be used singly or in combination of two or more. The curing accelerator preferably has a weight ratio [(G)/(X)] of 0.5/9.5 to 9.5/0.5 (more than Preferably 1/9 to 9/1) Thereby, the curability is further enhanced, and sufficient adhesion to the base material and the topcoat material can be obtained.

The coating material of the present invention may contain various components in addition to the components described above to such an extent that the effect of the present invention is not affected. Examples of such components include plasticizers, preservatives, antifungal agents, anti-algae agents, defoaming agents, leveling agents, pigment dispersants, thickeners, anti-skinning agents, dehydrating agents, matting agents, UV absorbers, silane coupling agents, light stabilizers, antioxidants, catalysts, and the like. Moreover, the resin component other than the said (A) component may be included. The coating material of the present invention comprises the above components (A) to (D) (preferably components (A) to (G)) as constituent components, and if necessary, these components are uniformly stirred and mixed by a conventional method. can be manufactured by Moreover, it is desirable to use the dressing material of the present invention in the form of a one-liquid type.

The coating material of the present invention can be preferably applied as an undercoat material to a base material or an old coating film.
Examples of base materials include concrete, mortar, slate plates, calcium silicate plates, ALC plates, extrusion molded plates, slate tiles, cement tiles, new tiles, porcelain tiles, siding boards, metals, glass, wood, and plywood. be done.

In addition, the old coating film is a coating film that is coated on the above base material. Glossy synthetic resin emulsion paint (JISK5660:2008), fireproof paint for construction (JISK5661:1970), synthetic resin emulsion paint (JISK5663:2008), road marking paint (JISK5665:2011), colorful pattern paint (JISK5667:2003) , synthetic resin emulsion pattern paint (JISK5668:2010), acrylic resin-based non-aqueous dispersion paint (JISK5670:2008), lead/chromium-free rust preventive paint (JISK5674:2008), high solar reflectance paint for roofs (JISK5675:2011) ), building floor paints (JISK5970:2008), architectural coating film waterproofing materials (JISA6021:2011), architectural finishing coating materials (JISA6909:2014), and the like. In particular, the present invention can be applied to fluororesin coating films, silicon resin coating films, and the like.

Various methods such as brush coating, roller coating, and spray coating can be employed for coating the coating material of the present invention. In the case of coating in a factory, a roll coater, flow coater, or the like can be used.

The coating amount of the coating material is preferably 0.1-0.6 kg/m ² (more preferably 0.2-0.5 kg/m ² ). The number of times of application may be appropriately set depending on the surface condition of the base material, etc., but is preferably 1 to 2 times. The drying time is preferably from 1 hour to 1 week. The drying temperature is preferably −10° C. or higher and 50° C. or lower (more preferably −5° C. or higher and 40° C. or lower).

In the present invention, a topcoat material can be applied after applying and drying the coating material. By applying a topcoat material, it is possible to protect the finished surface or improve aesthetics.

Various resins can be used as the resin component in the overcoat material. Examples of resin types include vinyl acetate resins, polyester resins, alkyd resins, vinyl chloride resins, epoxy resins, acrylic resins, urethane resins, acrylic silicon resins, fluorine resins, and composite resins thereof. Among these, one or more selected from acrylic resins, urethane resins, acrylic silicon resins, fluorine resins, and the like are suitable. Examples of forms of such resin components include water-soluble resins, water-dispersible resins (resin emulsions), solvent-soluble resins, solvent-free resins, non-water-dispersible resins, powder resins, and the like. Among them, one or more selected from aqueous topcoat materials such as water-soluble resins and water-dispersible resins, solvent-based (preferably weak solvent-based) topcoat materials such as solvent-soluble resins and non-aqueous-dispersible resins are suitable. . When the coating material of the present invention is used as an undercoat material, sufficient adhesion can be ensured even with a water-based topcoat material.

Such a topcoat material may contain various components other than the above components as long as the effects of the present invention are not significantly impaired. Examples of such components include thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreeze agents, pH adjusters, coloring pigments, extender pigments, aggregates, preservatives, and antifungal agents. , anti-algae agents, antibacterial agents, dispersants, antifoaming agents, adsorbents, fibers, cross-linking agents, UV absorbers, light stabilizers, antioxidants, anti-staining agents, hydrophilizing agents, water repellents, catalysts, Examples include solvents, water, and the like. The topcoat material of the present invention can be produced by uniformly mixing the resin component and, if necessary, the various components described above according to a conventional method. The form of the overcoat material can be, for example, a one-component type, a two-component type, or a multiple-component type.

A known coating tool can be used for coating the topcoat material. Examples of coating tools that can be used include sprays, rollers, and brushes.
The amount of topcoat material to be applied may be appropriately set according to the surface shape of the existing wall surface, the type of topcoat material, the type of coating equipment, etc., but is preferably 0.1 to 0.5 kg/m ² (more preferably 0.2 to 0.4 kg/m ² ). At the time of painting, the topcoat material can be diluted as needed.

Examples are shown below to further clarify the features of the present invention.
<Manufacturing of covering material>
According to the composition shown in Table 1, each component was mixed and stirred by a conventional method to obtain a coating material.

In addition, the raw materials shown below were used.
(A) Resin component/Resin 1: non-aqueous acrylic resin [acrylic styrene resin, hydroxyl value: 40 mgKOH/g, acid value: 2 mgKOH/g, weight average molecular weight: 70,000, glass transition temperature: 40°C, solid content : 50% by weight, medium: mineral spirit (aniline point 42°C)]
・ Resin 2: Non-aqueous dispersion type acrylic resin [alkyd resin-modified acrylic styrene resin, hydroxyl value: 40 mg KOH / g, acid value: 2 mg KOH / g, weight average molecular weight: 70,000, glass transition temperature 40 ° C., solid content: 50 % by weight, modification rate of alkyd resin: 1% by weight, medium: mineral spirit (aniline point 42° C.)]
・Resin 3: Soluble acrylic resin
[Alkyd resin-modified acrylic styrene resin, hydroxyl value: 0 KOHmg/g, acid value: 3 mgKOH/g, weight average molecular weight: 50,000, glass transition temperature: 41°C, solid content: 50% by weight, alkyd resin modification rate: 10% by weight , medium: mineral spirits (aniline point 42°C)]
・Resin 4: Soluble acrylic resin
[Acrylic styrene resin, hydroxyl value: 0 KOHmg/g, acid value: 3 mgKOH/g, weight average molecular weight: 50,000, glass transition temperature: 41°C, solid content: 50% by weight, alkyd resin modification rate: 0% by weight, medium: Mineral spirit (aniline point 42°C)]
(B) Aliphatic hydrocarbon-containing non-aqueous solvent/mineral spirit (aniline point 42°C)
(C) Polyisocyanate compound/Polyisocyanate compound 1 [hexamethylene diisocyanate derivative solution, solid content: 100% by weight, isocyanate group content: 21% by weight]
· Polyisocyanate compound 2 [hexamethylene diisocyanate derivative solution, solid content: 100% by weight, isocyanate group content: 12% by weight]
(D) Amine compound Amine 1: urea compound [ethylene urea content: 20% by weight, medium: methanol]
Amine 2: hydrazides [adipic acid dihydrazide content: 20% by weight, medium: methanol]
(E) Coloring pigment/rutile titanium oxide (average particle size: 0.3 μm, specific gravity: 4.2)
(F) Extender pigment, calcium carbonate (average particle size: 10 to 20 μm, specific gravity 2.7)
(G) Organometallic compound/Organic metal 1: cobalt octylate/mineral spirit solution [active ingredient: 80% by weight, amount of Co: 12% by weight]
(others)
・Curing accelerator [1,10-phenanthroline]
(Additive)
・Antifoaming agents, thickeners, dispersants, etc.

(Examples 1 to 11, Comparative Examples 1 to 3)
Using each obtained coating material, the following evaluations were carried out.
<Adhesion evaluation 1>
On a siding board on which an inorganic clear coating film is formed as an existing coating film, the coating material is applied so that the coating amount is 0.30 kg / m ² , and under standard conditions (temperature 23 ° C, relative humidity 50%) A specimen [I] dried for 24 hours was prepared.
Adhesion of the prepared test piece [I] was evaluated by a cross-cut tape method according to JIS K 5600-5-6.
Evaluation criteria are as follows.
AA: less than 5% defect area A: 5% or more and less than 10% defect area AB: 10% or more and less than 25% defect area B: 25% or more and less than 40% defect area C: defect area is 40% or more and less than 55% D: defect area is 55% or more

<Adhesion evaluation 2>
On a siding board on which an inorganic clear coating film is formed as an existing coating film, the coating material is applied so that the coating amount is 0.30 kg / m ² , and under standard conditions (temperature 23 ° C, relative humidity 50%) Dry for 24 hours, then apply a water-based topcoat material (acrylic silicone resin emulsion paint) so that the coating amount is 0.20 kg / m ² , and dry for 24 hours in a 50 ° C. environment [II ] was made.
The produced test sample [II] was evaluated by the same method as the adhesion evaluation 1.

<Adhesion evaluation 3>
After the prepared specimen [II] was immersed in water at 20°C for 3 days, the specimen was taken out and dried (23°C, 3 hours). observed and evaluated.
The evaluation criteria were a four-grade evaluation (A>B>C>D), with "A" indicating almost no abnormality and "D" indicating abnormality.

Good adhesion was obtained in Examples 1-11. In particular, in Examples 2 to 6 and 10, excellent adhesion to both the substrate and the aqueous topcoat material could be obtained.

Claims (3)

Constituent components include a resin component (A), an aliphatic hydrocarbon-containing non-aqueous solvent (B), a polyisocyanate compound (C), and an organic amine compound (D),
The resin component (A) includes a non-aqueous dispersion resin (A-1) and a soluble resin (A-2),
A coating material, wherein the non-aqueous-dispersible resin (A-1) and/or the soluble resin (A-2) have a hydroxyl group. As a component, it contains an extender pigment,
2. The coating material according to claim 1, comprising 50 to 600 parts by weight of the extender pigment with respect to 100 parts by weight of the solid content of the resin component (A). The solid content weight ratio [(A-1)/(A-2)] between the non-aqueous dispersion type resin (A-1) and the soluble resin (A-2) is 2/98 to 80/20. The covering material according to claim 1 or 2, characterized in that: