JP7366674B2 - Covering material - Google Patents

Description

The present invention relates to a novel dressing.

BACKGROUND ART Buildings, civil engineering structures, etc. are painted with various paints for the purpose of protecting their frames and improving their aesthetic appearance. However, in recent years, in urban areas, oil-based pollutants and the like are floating in the air due to exhaust gas from automobiles, etc., and the surface of the coating film is likely to be contaminated by these pollutants.

On the other hand, various techniques have been proposed to incorporate silicate compounds into paints as techniques for improving stain resistance. For example, JP-A-2005-263839 (Patent Document 1) discloses an isocyanate-curable coating composition that combines an alkoxysilane compound containing a mercapto functional group, an organosilicate compound, and an organotin catalyst. For such two-component paints, it is important to ensure a sufficient pot life. However, the examples in Cited Document 1 only disclose clear paints, and there is still room for improvement in ensuring a sufficient pot life when powder components such as pigments are included.

Japanese Patent Application Publication No. 2005-263839

The present invention was made in view of the above circumstances, and provides a coating material comprising a polyol compound, a pigment-containing main ingredient, and a polyisocyanate compound-containing curing agent that ensures a sufficient pot life and has excellent coating film properties. The purpose is to express the

The present inventors have conducted extensive research in view of the problems of the prior art as described above, and have found that, in a coating material consisting of a main material containing a polyol compound and a pigment, and a curing agent containing a polyisocyanate compound, the main material and the curing agent are They came up with the idea that each of them contains a specific silane compound, and completed the present invention.

That is, the present invention has the following features.
1. A coating material consisting of a main agent and a curing agent,
The above main ingredient contains (A) a polyol compound, (B) a pigment, (C) an alkoxysilane compound, and (D) an aliphatic hydrocarbon-containing nonaqueous solvent (provided that alkylene oxide having 2 to 40 repeating units) (excluding those containing alkoxysilane compounds with a weight average molecular weight of 150 to 3,500 containing chains),
The coating material is characterized in that the curing agent contains (E) a polyisocyanate compound and (F) a tetraalkoxysilane compound.
2. 1. The alkoxysilane compound (C) contains tetraalkoxysilane and/or alkylalkoxysilane. Covering material described in.

According to the present invention, the stability (pot life) when mixing the base agent and curing agent is excellent, and stable effects are sufficiently exhibited in various physical properties of the coating film (e.g., color, gloss, stain resistance, etc.). be able to.

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

The coating material of the present invention consists of a main agent and a curing agent, and the main agent contains (A) a polyol compound, (B) a pigment, (C) an alkoxysilane compound, and (D) an aliphatic hydrocarbon-containing nonaqueous solvent. , the curing agent is characterized in that it contains (E) a polyisocyanate compound and (F) a tetraalkoxysilane compound.

(base agent)
The main ingredient is characterized by containing (A) a polyol compound, (B) a pigment, (C) an alkoxysilane compound, and (D) an aliphatic hydrocarbon-containing nonaqueous solvent.

(A) Polyol compounds (hereinafter also referred to as "component (A)") include, for example, polyether polyols, polyester polyols, acrylic polyols, fluorine-containing polyols, etc. In addition, phenol resin polyols, epoxy polyols, polybutadiene polyols, etc. It is also possible to use polyisoprene polyols, polyester-polyether polyols, urea-dispersed polyols, carbonate polyols, and the like. As component (A), one or more of these can be used, and among these, it is desirable to include an acrylic polyol.

Examples of polyether polyols include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, glucose, sorbitol, and sucrose, as well as propylene oxide, ethylene oxide, and butylene oxide. and polyols obtained by adding styrene oxide and the like.

Examples of polyester polyols include polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, trimethylolpropane, and pentaerythritol; glutaric acid, adipic acid, pimelic acid; Examples include condensation polymers with polycarboxylic acids such as superic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, and hydrogenated dimer acid.

As the acrylic polyol, a copolymer of a (meth)acrylic acid alkyl ester, a hydroxyl group-containing monomer, and other monomers as necessary can be used. Among these, (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, Examples of hydroxyl group-containing monomers such as cyclohexyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and ) Hydroxy alkyl esters of (meth)acrylic acid such as 2-hydroxybutyl acrylate and 4-hydroxybutyl (meth)acrylate; hydroxyalkyl esters such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxypentyl vinyl ether, etc. Vinyl ether: Hydroxyallyl ethers such as ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, etc. can be mentioned, and one or more of these can be used.

Other monomers constituting the acrylic polyol include, for example, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylamino (meth)acrylate, aminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate. Amino group-containing monomers such as acrylate; carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or its monoalkyl ester, itaconic acid or its monoalkyl ester, fumaric acid or its monoalkyl ester; (meth) Amide-containing monomers such as acrylamide and ethyl (meth)acrylamide; Nitrile group-containing monomers such as (meth)acrylonitrile; Epoxy group-containing monomers such as glycidyl (meth)acrylate; Aromatics such as styrene, methylstyrene, chlorostyrene, vinyltoluene, etc. Hydrocarbon monomers include vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl pivalate, and one or more of these may be used as required.

A fluorine-containing polyol is a compound having a fluorine atom and a hydroxyl group in its resin skeleton. The fluorine-containing polyol can be obtained, for example, by copolymerizing a fluorine-containing monomer such as a fluoroolefin monomer or a fluoroalkyl group-containing acrylic monomer, a hydroxyl group-containing monomer, and other polymerizable monomers as necessary. .

Examples of the fluoroolefin monomer include perfluoroolefins such as tetrafluoroethylene, chlorotrifluoroethylene, and hexafluoropropylene; vinyl fluoride, vinylidene fluoride, and the like. Examples of the fluoroalkyl group-containing acrylic monomer include perfluoromethyl methacrylate, perfluoroisononylmethyl methacrylate, 2-perfluorooctylethyl acrylate, and 2-perfluorooctylethyl methacrylate.

As the hydroxyl group-containing monomer, the same hydroxyl group-containing monomers as those constituting the acrylic polyol can be used. Further, as other polymerizable monomers, the same monomers as those constituting the above-mentioned acrylic polyol can be used.

The hydroxyl value of component (A) is preferably 10 to 200 KOHmg/g (more preferably 20 to 100 KOHmg/g). The hydroxyl value is a value expressed by the number of mg of potassium hydroxide equivalent in mole to the hydroxyl group contained in 1 g of sample, and is based on JIS K 1557-1:2007 Plastics - Polyurethane raw material polyol test method - Part 1: Hydroxyl group This is the value measured based on the method of calculating the value. In the present invention, "α to β" is synonymous with "above α and below β".

In the present invention, it is preferable to contain (A-1) a polyol compound having an amino group and/or a carboxyl group (hereinafter also referred to as "component (A-1)") as component (A). By containing one or more of such components (A-1), the effects of the present invention can be further enhanced.
Examples of (A-1) include polyols having an amino group, polyols having a carboxyl group, polyols having an amino group and a carboxyl group, and one or more of these can be used. For example, embodiments containing a polyol compound having an amino group and a polyol compound having a carboxyl group as component (A-1) are also suitable.

As component (A-1), for example, a copolymer of an amino group-containing monomer and/or a carboxyl group-containing monomer can be used. As component (A-1) in the present invention, an acrylic polyol having an amino group and/or a carboxyl group is particularly suitable. Such acrylic polyols include those using amino group-containing monomers and/or carboxyl group-containing monomers among the other monomers mentioned above, that is, at least (meth)acrylic acid alkyl esters, hydroxyl group-containing monomers, and amino group-containing monomers. Copolymerized monomers and/or carboxyl group-containing monomers can be used.

The ratio of the amino group-containing monomer in component (A-1) is preferably 0.1 to 40% by weight (more preferably 0.5 to 30% by weight or less) among the constituent components of component (A-1). .

(Meth)acrylic acid is particularly suitable as the carboxyl group-containing monomer in component (A-1). The proportion of the carboxyl group-containing monomer is preferably 0.1 to 40% by weight (more preferably 0.5 to 20% by weight or less) in the constituent components of component (A-1).

The amine value of the component (A-1) is preferably 0.01 to 20 KOHmg/g or less (more preferably 0.1 to 10 KOHmg/g or less. The amine value is determined by titrating the sample with perchloric acid. It is the amount of base identified as amine expressed in milligrams (mg) of potassium hydroxide in 1 g. (Nitrogen content and total amine value display).

The acid value of component (A-1) is preferably 0.1 to 10 KOHmg/g or less (more preferably 1 to 8 KOHmg/g or less). The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid component present in 1 g of sample, and is based on JIS K 5601-2-1:1999 Paint component testing method "Acid value (titration method)". This is the value measured based on ``.

Component (A) includes solvent-soluble resins, non-water-dispersible resins, etc., and these can also be used in combination.

The (B) pigment (hereinafter also referred to as "(B) component") includes (B-1) colored pigment (hereinafter also referred to as "(B-1) component") to express various colors. It becomes possible to do so.

As component (B-1), chromatic pigments, white pigments, black pigments, etc. can be used. Among these, chromatic pigments are pigments exhibiting chromatic colors such as yellow, orange, red, green, blue, and violet. Examples of such chromatic pigments include inorganic pigments such as ferric oxide, hydrous ferric oxide, ultramarine blue, cobalt blue, and cobalt green, azo pigments, naphthol pigments, pyrazolone pigments, anthraquinone pigments, perylene pigments, Examples include organic substances such as quinacridone series, disazo series, isoindolinone series, benzimidazole series, phthalocyanine series, and quinophthalone series. On the other hand, the white pigment is a pigment exhibiting white color, and includes, for example, titanium oxide, zinc oxide, aluminum oxide, and the like. The black pigment is a pigment that exhibits black color, and includes, for example, iron black, iron-manganese composite oxide, iron-copper-manganese composite oxide, iron-chromium-cobalt composite oxide, copper-chromium composite oxide, and copper-chromium composite oxide. Examples include inorganic materials such as manganese-chromium composite oxide, and carbon black. These can be used alone or in combination of two or more. Further, the surface thereof may be subjected to some kind of treatment.

In the present invention, as the component (B), an extender pigment (B-2) (hereinafter also referred to as "component (B-2)") can also be mixed. (B-2) Ingredients include, for example, heavy calcium carbonate, light calcium carbonate, kaolin, clay, china clay, china clay, diatomaceous earth, hydrous fine silicic acid, talc, barite powder, barium sulfate, precipitated barium sulfate, carbonic acid Examples include barium, magnesium carbonate, silica powder, and aluminum hydroxide. These can be used alone or in combination of two or more. Component (B-2) can be used, for example, for the purpose of adjusting solid content, adjusting viscosity, adjusting gloss (reducing gloss, etc.), or improving storage stability and pigment compatibility.

The mixing ratio of component (B) is preferably 1 to 300 parts by weight (more preferably 5 to 250 parts by weight) based on 100 parts by weight of the solid content of component (A). Furthermore, the amount of component (B-1) is preferably 1 to 200 parts by weight (more preferably 5 to 150 parts by weight) based on 100 parts by weight of the solid content of component (A). When using component (B-2), the amount of component (B-2) is preferably 100 parts by weight or less (more preferably 1 to 80 parts by weight) based on 100 parts by weight of the solid content of component (A). .

(C) Alkoxysilane compounds (hereinafter also referred to as "component (C)") include (C-1) tetraalkoxysilane compounds, (C-2) alkylalkoxysilane compounds, (C-3) silane coupling agents, etc. Alternatively, one or more compounds selected from these compounds (for example, condensates, modified products, polymers, copolymers, etc.) can be used. By including component (C), a sufficient pot life can be ensured, and various physical properties of the coating film (for example, color, gloss, stain resistance, etc.) can be improved. Its mechanism of action is not limited to the following, but in the main agent, component (C) is distributed (orientated) near the surface of component (B), thereby increasing the dispersion stability of component (B). be able to. Furthermore, since the component (C) is present near the component (B) when the curing agent is mixed, the reaction (aggregation) between the component (B) and the tetraalkoxysilane (F) can be suppressed. As a result, it is possible to have excellent mixing stability when mixing the base agent and curing agent, to ensure a sufficient pot life, and to optimize the effect of tetraalkoxysilane (F) within the pot life. Excellent physical properties of the coating film can be obtained.

As the (C-1) tetraalkoxysilane compound (hereinafter also referred to as "component (C-1)"), tetraalkoxysilanes, condensates of tetraalkoxysilanes, modified products thereof, and the like can be used. Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraisobutoxysilane, tetra sec-butoxysilane, tetra t-butoxysilane, and tetra Examples include phenoxysilane, monoethoxytrimethoxysilane, monobutoxytrimethoxysilane, monopentoxytrimethoxysilane, monohethoxytrimethoxysilane, dimethoxydiethoxysilane, and dimethoxydibutoxysilane. These can be used alone or in combination of two or more.

(C-2) Alkylalkoxysilane compounds (hereinafter also referred to as "component (C-2)") include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane. Silane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane , dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, methyl Examples include phenyldimethoxysilane and methylphenyldiethoxysilane. These may be used alone or in combination of two or more, but it is particularly preferable to include an alkyl alkoxysilane compound in which the alkyl group has 1 to 10 carbon atoms.

(C-3) Examples of the silane coupling agent include γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyltriethoxysilane, β-(3,4epoxycyclohexyl)ethyltrimethoxysilane, etc. of amino group-containing silane coupling agents such as epoxy group-containing silane coupling agents, N-β (aminoethyl) γ-aminopropylmethyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ-aminopropyltriethoxysilane. Other examples include isocyanate group-containing silane coupling agents, isocyanurate group-containing silane coupling agents, acid anhydride group (carboxyl group)-containing silane coupling agents, and the like. These can be used alone or in combination of two or more.

In the present invention, it is preferable that the component (C) contains one or more selected from the above-mentioned (C-1) component and/or the above-mentioned (C-2) component. Thereby, the above effects can be further enhanced. The mixing ratio of component (C) is preferably 0.05 to 30 parts by weight (more preferably 0.1 to 20 parts by weight) per 100 parts by weight of the solid content of component (A).

The coating material of the present invention is a so-called weak solvent type material containing (D) an aliphatic hydrocarbon-containing non-aqueous solvent (hereinafter also referred to as "component (D)"). Component (D) is a non-aqueous solvent that is less toxic than toluene, xylene, etc., has high operational safety, and has less influence on air pollution. Examples of aliphatic hydrocarbons include n-hexane, n-pentane, n-octane, n-nonane, n-decane, n-undecane, and n-dodecane. These can be used alone or in combination of two or more. In the present invention, aliphatic hydrocarbons can also be introduced by using a mixed solvent such as mineral spirits. 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 component (D).

Component (D) may contain a solvent that is miscible with an aliphatic hydrocarbon. Examples of such solvents include petroleum-based solvents such as petroleum ether, petroleum naphtha, and solvent naphtha, as well as ethyl acetate, butyl acetate, methyl ethyl ketone, and methyl isobutyl ketone. Suitable solvents include, for example, mixed aniline. Examples include petroleum solvents (petroleum mixed solvents containing aromatic hydrocarbons) having an aniline point of 12 to 70°C. Note that the mixed aniline point or aniline point is a value measured by the method of JIS K2256:2013.

The mixing ratio of component (D) 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 component (A), from the viewpoint of workability during overcoating, finish quality, etc. parts by weight). Note that component (D) also includes a solvent used as a medium for each component.

The main ingredient of the present invention can be produced by uniformly stirring and mixing the above components (A) to (D) in a conventional manner. For example, after preparing a mill base by mixing part of component (A), component (B), component (C), and part of component (D), the remainder of component (A) and (D) are mixed into the mill base. ) can be produced by mixing (reddown) the remaining components. This increases the dispersibility of the component (B) and further enhances the effects of the present invention.

(hardening agent)
The curing agent is characterized by containing (E) a polyisocyanate compound and (F) a tetraalkoxysilane compound.

(E) The polyisocyanate compound (hereinafter also referred to as "component (E)") has two or more isocyanate groups in one molecule and reacts with the component (A) to form a coating film. be. Component (E) is preferably one that can crosslink with component (A) at room temperature. Note that the normal temperature here refers to approximately -10°C or more and 50°C or less, preferably 5°C or more and 40°C or less.

Component (E) includes, for example, toluene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (pure-MDI), polymeric MDI, xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), water Isocyanate monomers such as doped XDI and hydrogenated MDI are derivatized by alphanatization, biuretization, dimerization (uretidiionization), trimerization (isocyanuration), adductization, carbodiimidation reactions, etc., and mixtures thereof. can be mentioned. These can be used alone or in combination of two or more.

In the present invention, the isocyanate group content of component (E) is preferably 2 to 40% by weight (more preferably 3 to 30% by weight). In the present invention, the isocyanate group content is defined as the content (wt%) of isocyanate groups contained in the solid content of the polyisocyanate compound, and after neutralizing the isocyanate groups with an excess of amine, This value is determined by back titration.

The mixing ratio of component (E) may be set in consideration of the NCO/OH equivalent ratio to the hydroxyl group of component (A). The NCO/OH equivalent ratio of the hydroxyl group of component (A) and the isocyanate group of component (E) is preferably 0.6 to 1.4 (more preferably 0.8 to 1.2). With such a ratio, the effects of the present invention can be further enhanced.

(F) The tetraalkoxysilane compound (hereinafter also referred to as "component (F)") mainly has the effect of imparting hydrophilicity to the formed film.As such component (F), the above-mentioned (C) ) The same tetraalkoxysilanes, condensates of tetraalkoxysilanes, and modified products thereof can be used, but in the present invention, (F-1) an alkoxyl group having 1 or more carbon atoms and 2 or less carbon atoms; It is preferable to use a condensate of tetraalkoxysilane containing an alkoxyl group of 3 or more and 12 or less (hereinafter referred to as "component (F-1)").In particular, as component (F-1), the compound It is preferable that 5% by weight or more and 50% by weight or less of the total alkoxyl groups be alkoxyl groups having 3 or more and 12 or less carbon atoms.

Examples of the alkoxyl group having 3 or more and 12 or less carbon atoms include direct groups such as n-propoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, n-octyloxy group, and n-dodecyloxy group. Chain alkoxy group, isopropoxy group, isobutoxy group, t-butoxy group, sec-butoxy group, isopentyloxy group, neopentyloxy group, isohexyloxy group, 3-methylpentyloxy group, 1-methylhexyloxy group, Branched alkoxyl groups such as 1-ethylpentyloxy group, 2,3-dimethylbutoxy group, 1,5-dimethylhexyloxy group, 2-ethylhexyloxy group, 1-methylheptyloxy group, t-octyloxy group, etc. It will be done.

Such component (F-1) can be produced by a known method. Examples of the method for producing component (F-1) include a method in which a tetraalkoxysilane condensate having an alkoxyl group having 1 to 2 carbon atoms is modified with an alcohol having 3 to 12 carbon atoms.

The mixing ratio of component (F) is preferably 0.1 to 50 parts by weight (more preferably 1 to 30 parts by weight) in terms of SiO ₂ based on 100 parts by weight of the resin solid content of component (A). When the content of component (F) is within this range, an excellent contamination suppressing effect etc. can be obtained.

In the present invention, SiO ₂ equivalent refers to the weight that remains as silica (SiO ₂ ) when a compound with an Si-O bond such as an alkoxysilane is completely hydrolyzed and then fired at 900°C. It is expressed as follows. Generally, alkoxysilanes have the property of reacting with water to undergo a hydrolysis reaction to form silanol, and further to cause a condensation reaction between silanols or between silanol and alkoxy. When this reaction is carried out to its ultimate extent, it becomes silica (SiO ₂ ). These reactions are
RO(Si(OR) _2O )nR+(n+1) _H2O → _nSiO2 +(2n+2)ROH (R represents an alkyl group. n is an integer.)
It is expressed by the reaction formula. The SiO ₂ conversion in the present invention is calculated by converting the amount of the remaining silica component based on this reaction formula.

The curing agent of the present invention can be produced by uniformly stirring and mixing the above components (E) to (F) using a conventional method.

(Coating material)
The coating material of the present invention can be produced by uniformly stirring and mixing the above-mentioned main ingredient and curing agent by a conventional method.
Further, the coating material of the present invention may contain various components in addition to the above-mentioned components in the base agent and/or curing agent to the extent that they do not affect the effects of the present invention. Such components include, for example, catalysts, plasticizers, preservatives, antifungal agents, algaecides, antifoaming agents, leveling agents, pigment dispersants, thickeners, antiskinning agents, dehydrating agents, and matting agents. agents, ultraviolet absorbers, light stabilizers, antioxidants, solvents, etc. Moreover, it may contain resin components other than the above-mentioned (A) component.

The coating material 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, ALC, gypsum board, perlite board, tile, glass board, wood board, plastic board, metal board, etc. It will be done. These base materials may be those that have been subjected to some kind of surface treatment (filler treatment, putty treatment, surfacer treatment, sealer treatment, etc.) or those that have already been coated with a coating film.

The coating material of the present invention can be diluted during coating. As the diluent, the above-mentioned component (D) is preferable, and it is desirable to dilute the component (D) within a range in which the total amount of the component (D) after dilution satisfies the above-mentioned mixing ratio.

Various methods can be used as the coating method, such as brush coating, roller coating, and spray coating. The coating amount during coating is preferably 30 to 250 g/m ² , more preferably 50 to 200 g/m ² per coating. Moreover, once the coating is applied and the coating film dries, the next coating (overcoating) can be performed. The drying temperature is preferably -10 to 50°C, more preferably -5 to 40°C. The number of times of coating is preferably two or more times.

Examples are shown below to clarify the features of the present invention.
(A) Polyol compound/carboxyl group/amino group-containing acrylic polyol compound solution (solid content: 50% by weight, hydroxyl value: 40KOHmg/g, acid value: 4KOHmg/g, amine value: 2KOHmg/g, medium: mineral spirit)
(B) Pigment/rutile type titanium oxide
(C) Alkoxysilane compound/(C-1) Tetramethoxysilane/(C-2) Phenyltrimethoxysilane/dimethoxymethylphenylsilane mixture (D) Aliphatic hydrocarbon-containing non-aqueous solvent/Mineral spirit (E) Polyisocyanate Compound/hexamethylene diisocyanate derivative solution (solid content: 100% by weight, isocyanate group content: 20% by weight)
(F) n-butyl alcohol modified product of tetraalkoxysilane compound/tetramethoxysilane compound (average degree of condensation 4, transesterification rate 30%, residual silica ratio 40%)

(Manufacture of base agent)
・Main agent 1
200 parts by weight of component (A), 80 parts by weight of component (B), 1.5 parts by weight of component (C-1), 30 parts by weight of component (D), and 15 parts by weight of additives (antifoaming agent, thickener, etc.) Parts by weight were mixed and stirred to produce base ingredient 1.
・Main agent 2
200 parts by weight of component (A), 80 parts by weight of component (B), 1.5 parts by weight of component (C-2), 30 parts by weight of component (D), and 15 parts by weight of additives (antifoaming agent, thickener, etc.) Parts by weight were mixed and stirred to produce base ingredient 2.
・Main agent 3
200 parts by weight of component (A), 80 parts by weight of component (B), 30 parts by weight of component (D), and 15 parts by weight of additives (antifoaming agent, thickener, etc.) are mixed and stirred to produce main ingredient 3. did.

(Manufacture of curing agent)
Curing agent 1 was prepared by mixing and stirring 40 parts by weight of component (E), 20 parts by weight of component (F), and 40 parts by weight of a petroleum solvent.

(Manufacture of covering material)
According to the combinations of the main agent and curing agent shown in Table 1, the main agent and the curing agent were mixed so that the NCO/OH equivalent ratio was 1.0, a coating material was manufactured, and the following evaluation was performed.

(Examples 1-2, Comparative Example 1)
・Test specimen preparation: An epoxy base coat material was applied to a 300 mm x 150 mm x 1 mm aluminum plate so that the dry film thickness was 30 μm, and it was dried under standard conditions (temperature 23°C, relative humidity 50%) for 8 hours. The material was used as a base material.
Each coating material obtained by the above method was applied to the above substrate so that the dry film thickness was 40 μm (I) immediately after mixing, (II) after 1 hour of mixing, and (III) after 6 hours of mixing. and dried under standard conditions for 7 days to produce test specimens (I), test specimens (II), and test specimens (III).

-Evaluation of stain resistance Each test specimen was installed in Osaka Prefecture facing south at an angle of 30 degrees to the horizontal plane, and the stain resistance was evaluated after being exposed for one year. The evaluation was made on a four-level scale: excellent: A>B>C>D: poor. The results are shown in Table 2.

- Hue Stability The hue of the test specimen (I) was used as a blank, and the hue change in the test specimen (II) and the test specimen (III) was evaluated. The evaluation criteria were 4 grades (excellent: A>B>C>D: poor), with "A" indicating no change in hue and "D" indicating a clear change in hue. The results are shown in Table 2.

Claims (2)

A coating material consisting of a main agent and a curing agent,
The above main ingredient contains (A) a polyol compound, (B) a pigment, (C) an alkoxysilane compound, and (D) an aliphatic hydrocarbon-containing nonaqueous solvent (provided that alkylene oxide having 2 to 40 repeating units) (excluding those containing alkoxysilane compounds with a weight average molecular weight of 150 to 3,500 containing chains),
The coating material is characterized in that the curing agent contains (E) a polyisocyanate compound and (F) a tetraalkoxysilane compound. The coating material according to claim 1, wherein the alkoxysilane compound (C) contains tetraalkoxysilane and/or alkylalkoxysilane.