Covering material

Abstract

To provide a coating material capable of forming a coating film which has sufficient stain resistance and is excellent in crack resistance (bending resistance), followability, and the like.SOLUTION: The coating material of the present invention comprises a main agent and a curing agent. The main agent contains a polyol compound (A). The curing agent contains a polyisocyanate compound (B) and a silicate compound (C). The polyisocyanate compound (B) contains a polyisocyanate compound (b1) having an isocyanate group content of less than 14 wt.% and a polyisocyanate compound (b2) having an isocyanate group content of 14 wt.% or more.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a coating material.

Background Art

[0002] Conventionally, paint finishing has been carried out for protecting structures such as buildings and civil engineering structures, imparting designability and improving aesthetic appearance, and durable coating materials such as fluororesin-based, acrylic silicone resin-based and polyurethane resin-based ones have been widely adopted. However, due to their durability, these durable coating materials may rather cause the problem of contamination on the coating surface. Particularly, in places where a large amount of automobile exhaust gas and the like floats in the atmosphere, oily contaminants adhere to the coating surface and cause streak-like contamination (hereinafter referred to as "rain streak contamination"), and there have been cases where the paint finishing, which was supposed to be applied for improving urban landscape, becomes meaningless.

[0003] In response to this, various coating materials have been proposed, which make the coating surface hydrophilic, and peel off and wash away adhered oily contaminants by the action of rainwater spreading on the coating surface during rainfall. For example, Japanese Patent Application No. Hei 6-506632 (International Publication WO94 / 06870) proposes mixing an organosilicate into a coating material.

Prior Art Literature

Patent Literature

[0004]

Patent Literature 1

Summary of the Invention

Problem to be Solved by the Invention

[0005] However, when an organosilicate is further added to a durable coating material, although contamination resistance is improved, the formed coating tends to become hard, and depending on the type of the substrate, there has been a risk of causing problems such as cracking and decreased followability.

[0006] The present invention has been made in view of these points, and aims to provide a coating material that has sufficient stain resistance, as well as improved crack resistance (flex resistance) and conformability. [Means for solving the problem]

[0007] To solve these problems, the inventors, after diligent research, conceived of a coating material in which a specific polyisocyanate compound is an essential component, and thus completed the present invention.

[0008] In other words, the present invention has the following features. 1. A coating material having a main component and a hardening agent, The main component comprises a polyol compound (A), The polyol compound (A) contains a silicone component, and the content of the silicone component in the polyol compound (A) is 0.1 to 20% by weight in terms of SiO2 in the resin solids. The curing agent comprises a polyisocyanate compound (B) and a silicate compound (C). The polyisocyanate compound (B) is a hexamethylene diisocyanate having an isocyanate group content of less than 14% by weight. derivative (b1) and hexamethylene diisocyanate having an isocyanate group content of 14% by weight or more derivative (b2) Including, A coating material characterized in that the weight ratio of component (b1) to component (b2) [(b1) / (b2)] is 0.6 to 8. 2. The coating material according to 1, characterized in that the polyol compound (A) contains a silicone-containing polyol compound in component (A) at a concentration of 50 to 100% by weight on a solid content basis. 3. The hexamethylene diisocyanate is contained in the polyisocyanate compound (B). derivative The coating material according to 1, characterized by containing 20 to 90% by weight of (b1). 4. The silicate compound (C) is a condensate (c1) of a tetraalkoxysilane containing an alkoxyl group having 1 to 2 carbon atoms and an alkoxyl group having 3 to 12 carbon atoms, as described in 1. Covering material . 5. The coating material according to any one of claims 1 to 4, characterized in that it contains 0.1 to 50 parts by weight of the silicate compound (C) per 100 parts by weight of the solid content of the polyol compound (A). [Effects of the Invention]

[0009] According to the coating material of the present invention, it is possible to form a coating that has sufficient stain resistance, as well as excellent crack resistance (flex resistance) and conformability. [Modes for carrying out the invention]

[0010] The following describes embodiments for carrying out the present invention.

[0011] The coating material of the present invention comprises a main component and a curing agent, wherein the main component contains a polyol compound (A), and the curing agent contains a polyisocyanate compound (B) and a silicate compound (C).

[0012] (Main ingredient) The main component contains polyol compound (A).

[0013] Examples of polyol compounds (A) (hereinafter also referred to as "component (A)") include polyether polyols, polyester polyols, acrylic polyols, and fluorine-containing polyols. Other possibilities include phenol resin polyols, epoxy polyols, polybutadiene polyols, polyisoprene polyols, polyester-polyether polyols, urea-dispersed polyols, and carbonate polyols. One or more of these can be used as component (A), but it is preferable that it includes an acrylic polyol.

[0014] Acrylic polyols can be copolymerized with alkyl (meth)acrylates, hydroxyl group-containing monomers, and other monomers as needed. Examples of alkyl (meth)acrylates include 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, etc. Examples of hydroxyl group-containing monomers include 2-hydroxyethyl (meth)acrylate. Examples include hydroxyalkyl esters of (meth)acrylic acid such as (meth)acrylic acid-2-hydroxypropyl, (meth)acrylic acid-3-hydroxypropyl, (meth)acrylic acid-2-hydroxybutyl, and (meth)acrylic acid-4-hydroxybutyl; hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, and hydroxypentyl vinyl ether; and hydroxyallyl ethers such as ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, and triethylene glycol monoallyl ether. One or more of these can be used.

[0015] Other monomers that constitute acrylic polyols include, for example, amino group-containing monomers such as dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylamino (meth)acrylate, aminoethyl (meth)acrylate, and diethylaminoethyl (meth)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, and fumaric acid or its monoalkyl ester; amide-containing monomers such as (meth)acrylamide and ethyl (meth)acrylamide; nitrile group-containing monomers such as (meth)acrylonitrile; epoxy group-containing monomers such as glycidyl (meth)acrylate; aromatic hydrocarbon monomers such as styrene, methylstyrene, chlorostyrene, and vinyltoluene; and vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl pivalate. One or more of these can be used as needed.

[0016] Component (A) preferably further contains a silicone component (hereinafter, component (A) containing a silicone component is also referred to as a "silicone-containing polyol compound"). By including a silicone component, an improvement in long-term weather resistance can be obtained. Such silicone components can be in the form of chains, branches, rings, etc. The content of the silicone component is preferably 0.1 to 20% by weight (more preferably 0.5 to 10% by weight) in terms of SiO2 in the resin solids. In the above range, an improvement in long-term weather resistance can be obtained, and conformability to the substrate and adhesion can be ensured. In this invention, "α to β" is synonymous with "α or more and β or less".

[0017] In the present invention, the term "converted to SiO₂" refers to the expression by weight percentage of the silica (SiO₂) remaining when a compound having Si-O bonds is completely hydrolyzed and then calcined at 900°C. Generally, alkoxysilanes, silicates, silicones and the like have the property of reacting with water to undergo a hydrolysis reaction to form silanols, and further cause condensation reactions between silanols or between silanols and alkoxy groups. When this reaction proceeds to completion, silica (SiO₂) is formed. These reactions are RO(Si(OR)₂O)nR+(n+1)H₂O→nSiO₂+(2n+2)ROH (R represents an alkyl group, n is an integer) represented by the above reaction formula. The conversion to SiO₂ in the present invention is obtained by converting the amount of the remaining silica component based on this reaction formula.

[0018] The method for introducing silicone into component (A) is not particularly limited, and various methods can be adopted. For example: (1) a method of copolymerizing a silicone compound having a polymerizable double bond, (2) a method of reacting a functional group in a resin with a silicone compound having a functional group capable of reacting with said functional group, (3) a method of reacting a reactive silyl group-containing compound with a resin obtained by copolymerizing a reactive silyl group-containing monomer, (4) a method comprising reacting a functional group in a resin with a coupling agent having a functional group capable of reacting with said functional group, and then reacting the product with a reactive silyl group-containing compound; etc. These methods may be mentioned.

[0019] Examples of combinations of functional groups in the above (2) and (4) include hydroxyl group and isocyanate group, hydroxyl group and carboxylic acid anhydride group, amino group and isocyanate group, carboxyl group and epoxy group, amino group and epoxy group, and alkoxysilyl groups mutually, etc.

[0020] The reactive silyl groups in (3) and (4) above are those in which an alkoxyl group, phenoxy group, mercapto group, amino group, halogen, etc. are bonded to a silicon atom. As reactive silyl group-containing compounds, those having two or more reactive silyl groups in one molecule are used, for example, tetrafunctional alkoxysilanes such as tetraethoxysilane, tetramethoxysilane, and tetrabutoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and phenyltributoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dipropyldimethoxysilane, dipropyl Examples include difunctional alkoxysilanes such as diethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, methylphenyldimethoxysilane, and methylphenyldiethoxysilane; chlorosilanes such as tetrachlorosilane, methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane, and methylphenyldichlorosilane; and acetoxysilanes such as tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, and diphenyldiacetoxysilane. One or more of these can be used. Compounds having one reactive silyl group in a single molecule can also be used in combination.

[0021] The reactive silyl group-containing monomer in (3) above is a compound containing a reactive silyl group and a polymerizable double bond, and examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-butoxysilane, vinyltris(β-methoxyethoxy)silane, allyltrimethoxysilane, trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, triethoxysilylpropyl vinyl ether, γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane, γ-(meth)acryloyloxypropylmethyldimethoxysilane, vinylmethyldimethoxysilane, methyldimethoxysilylethyl vinyl ether, methyldimethoxysilylpropyl vinyl ether, etc., and one or more of these can be used.

[0022] The coupling agent in (4) above is, for example, a compound having at least one alkoxysilyl group and other substituents in one molecule. Specific examples of coupling agents include β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, isocyanate-functionalized silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, and γ-methacryloxypropyltriethoxysilane, and one or more of these can be used.

[0023] In the present invention, it is preferable that component (A) contains the above-mentioned silicone-containing polyol compound in an amount of 50 to 100% by weight (more preferably 50 to 99% by weight, and even more preferably 60 to 95% by weight) on a solid content basis. In this case, it is possible to obtain the effect of excellent film properties such as weather resistance.

[0024] The hydroxyl value (solid content) of component (A) is preferably 5 to 200 KOH mg / g (more preferably 10 to 180 KOH mg / g, and even more preferably 30 to 150 KOH mg / g). When the above range is met, excellent effects can be observed in various coating properties, stain resistance, etc. The hydroxyl value is a value expressed by the number of mg of potassium hydroxide equivalent to the hydroxyl groups contained in 1 g of the sample.

[0025] The glass transition temperature of component (A) is preferably -10 to 80°C (more preferably 0 to 60°C). If the glass transition temperature is within this range, the coating properties such as stain resistance, flexibility, and durability can be improved. The glass transition temperature is a value determined by Fox's formula based on the vinyl monomers constituting the resin.

[0026] Examples of component (A) include solvent-soluble resins and non-aqueous dispersible resins, and one or more of these can be used. In the present invention, it is preferable to include at least a non-aqueous dispersible resin, and it is even preferable to use a non-aqueous dispersible resin and a solvent-soluble resin in combination. Specific embodiments of component (A) using a combination of a non-aqueous dispersible resin and a solvent-soluble resin include, for example, • Non-aqueous dispersible polyol compounds and solvent-soluble polyol compounds, • Non-aqueous dispersible polyol compounds and solvent-soluble silicone-containing polyol compounds, • Non-aqueous dispersible silicone-containing polyol compounds and solvent-soluble polyol compounds, • Non-aqueous dispersible silicone-containing polyol compounds and solvent-soluble silicone-containing polyol compounds, Examples include the above. Furthermore, as the polyol compound of the above embodiment, an embodiment containing an acrylic polyol is preferred. This is advantageous in terms of stain resistance, flexibility, etc. A non-aqueous dispersible resin is one in which the above component (A) is dispersed as resin particles in a non-aqueous solvent. A solvent-soluble resin is one in which the above component (A) is dissolved in a non-aqueous solvent.

[0027] The non-aqueous solvent preferably contains an aliphatic hydrocarbon-containing non-aqueous solvent (a so-called weak solvent). Aliphatic hydrocarbon-containing non-aqueous solvents have lower toxicity than toluene, xylene, etc., offer higher safety during operation, and have less impact 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 individually or in combination of two or more. In this invention, aliphatic hydrocarbons can also be introduced by using a mixed solvent such as mineral spirits. The aliphatic hydrocarbon is preferably present in an amount of 5% by weight or more of the total amount of the non-aqueous solvent, and more preferably in an amount of 10 to 80% by weight.

[0028] Non-aqueous solvents may include solvents that are miscible with aliphatic hydrocarbons. 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, petroleum-based solvents (aromatic hydrocarbon-containing petroleum mixed solvents) with 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.

[0029] (Hardening agent) The curing agent comprises (B) a polyisocyanate compound and (C) a silicate compound.

[0030] (B) The polyisocyanate compound (hereinafter also referred to as "component (B)") has two or more isocyanate groups in one molecule and reacts with component (A) to form a coating. Component (B) is preferably one that can crosslink with component (A) at room temperature. Here, "room temperature" generally refers to a temperature between -10°C and 50°C, preferably between 5°C and 40°C.

[0031] (B) Component(s) include at least one diisocyanate selected from aliphatic diisocyanates and alicyclic diisocyanates, and alcohol components, and optionally polyol components, which are derivatized by alfanation, biuretation, dimerization (uretidioneation), trimerization (isocyanurateation), adductation, carbodiimideation, etc., and mixtures thereof. These can be used individually or in combination of two or more.

[0032] Aliphatic diisocyanates are compounds that have a saturated aliphatic group in their molecule, such as 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (also known as hexamethylene diisocyanate (HDI)), 1,6-diisocyanato-2,2,4-trimethylhexane, and methyl 2,6-diisocyanatohexanoate (lysine diisocyanate). On the other hand, alicyclic diisocyanates are compounds that have a cyclic aliphatic group in their molecule, such as 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), and 1,4-diisocyanatocyclohexane. Among these, HDI is the most preferred due to its excellent weather resistance and flexibility. (Hereafter, aliphatic diisocyanates and alicyclic diisocyanates will be collectively referred to as "diisocyanates.")

[0033] Examples of alcohol components include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, 1-pentanol, 2-pentanol, isoamyl alcohol, 1-hexanol, 2-hexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, 3,3,5-trimethyl-1-hexanol, tridecanol, pentadecanol, palmityl alcohol, stearyl alcohol, cyclopentanol, cyclohexanol, methylcyclohexanol, and trimethylcyclohexanol. These can be used individually or in combination of two or more.

[0034] Examples of polyol components include polyether polyols, polyester polyols, and polyolefin polyols. In the present invention, polyether polyols such as polypropylene triol, polypropylene glycol, and polytetramethylene glycol are particularly preferred. These can be used individually or in combination of two or more.

[0035] The present invention is characterized in that component (B) comprises a polyisocyanate compound (b1) having an isocyanate group content of less than 14% by weight (preferably 2% to 13% by weight) in the solid content, and a polyisocyanate compound (b2) having an isocyanate group content of 14% by weight or more (preferably 15% to 30% by weight, more preferably 16% to 28% by weight). By using components (b1) and (b2) in combination, excellent effects can be obtained in both stain resistance and flexibility. Furthermore, excellent effects can be obtained in terms of conformability to the substrate, and even in substrates having a sealant, excellent conformability can be obtained. In this invention, the isocyanate group content is defined as the content (by weight) of isocyanate groups contained in the solid content of the polyisocyanate compound, and is a value obtained by back titration with hydrochloric acid after neutralizing the isocyanate groups with an excess amine.

[0036] In the present invention, it is preferable that component (B) contains 20 to 90% by weight (more preferably 30 to 80% by weight, and even more preferably 45 to 75% by weight) of (b1). On the other hand, it is preferable that component (B) contains 10 to 80% by weight (more preferably 20 to 70% by weight, and even more preferably 25 to 55% by weight) of (b2). Furthermore, it is preferable that the weight ratio of component (b1) to component (b2) [(b1) / (b2)] is 0.5 or more (more preferably 0.6 to 8, even more preferably 0.7 to 5, and particularly preferably 1 to 3). In this range, the above effects can be further enhanced.

[0037] The mixing ratio of component (B) should be set considering the molar ratio [NCO] / [OH] between the isocyanate groups of component (B) and the hydroxyl groups of component (A). The molar ratio [NCO] / [OH] between the isocyanate groups of component (B) and the hydroxyl groups of component (A) is preferably 0.6 to 1.4 (more preferably 0.8 to 1.3). Such a ratio can further enhance the effects of the present invention.

[0038] The mixing ratio (weight ratio) of component (A) and component (B) is determined by the hydroxyl value of component (A) and the isocyanate group content of component (B). In the coating material of the present invention, the mixing ratio of component (B) is preferably 5 to 50 parts by weight (more preferably 10 to 40 parts by weight) per 100 parts by weight of the resin solids of component (A). If component (B) is within this range, the above NCO / OH molar ratio can be satisfied.

[0039] Silicate compound (C) (hereinafter also referred to as "component (C)") primarily serves to impart hydrophilicity to the formed film. Examples of such (C) components include tetraalkoxysilanes, condensates of tetraalkoxysilanes, and modified versions thereof. Examples of tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetrasec-butoxysilane, tetra-t-butoxysilane, tetraphenoxysilane, monoethoxytrimethoxysilane, monobutoxytrimethoxysilane, monopentoxytrimethoxysilane, monohethoxytrimethoxysilane, dimethoxydiethoxysilane, and dimethoxydibutoxysilane. These can be used individually or in combination of two or more.

[0040] In the present invention, it is preferable to use a condensate (c1) of a tetraalkoxysilane containing an alkoxyl group having 1 to 2 carbon atoms and an alkoxyl group having 3 to 12 carbon atoms (hereinafter referred to as "component (c1)"). In particular, it is preferable that component (c1) is such that 5% to 50% by weight of the total alkoxyl groups of the compound are alkoxyl groups having 3 to 12 carbon atoms.

[0041] Examples of alkoxy groups having 3 to 12 carbon atoms include linear alkoxy groups such as n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, n-octyloxy, and n-dodecyloxy groups, and branched alkoxy groups such as isopropoxy, isobutoxy, t-butoxy, sec-butoxy, isopentyloxy, neopentyloxy, isohexyloxy, 3-methylpentyloxy, 1-methylhexyloxy, 1-ethylpentyloxy, 2,3-dimethylbutoxy, 1,5-dimethylhexyloxy, 2-ethylhexyloxy, 1-methylheptyloxy, and t-octyloxy groups.

[0042] Such (c1) components can be produced by known methods. Examples of methods for producing (c1) include modifying a tetraalkoxysilane condensate having alkoxyl groups with 1 to 2 carbon atoms with an alcohol having 3 to 12 carbon atoms.

[0043] The mixing ratio of component (C) is preferably 0.1 to 50 parts by weight (more preferably 1 to 30 parts by weight) per 100 parts by weight of the resin solids of component (A). Excellent stain resistance and other effects can be obtained when component (C) is within this range.

[0044] Furthermore, the mixing ratio of component (B) and component (C) is preferably 5 to 80 parts by weight (more preferably 10 to 60 parts by weight) of component (C) per 100 parts by weight of solid content of component (B). If component (C) is within this range, excellent stain resistance and other effects can be obtained.

[0045] The curing agent of the present invention can be manufactured by uniformly stirring and mixing the above components (B) and (C) using conventional methods.

[0046] (covering material) The coating material of the present invention is a two-component coating material consisting of the above-mentioned main component and the above-mentioned hardener, and is used by uniformly stirring and mixing the main component and hardener by conventional methods during application. Furthermore, the coating material of the present invention may contain, in addition to the above-mentioned components, various other components in the main component and / or curing agent, to an extent that does not affect the effects of the present invention. Examples of such components include pigments, catalysts, plasticizers, preservatives, fungicides, algaecides, defoamers, leveling agents, pigment dispersants, thickeners, anti-skinning agents, dehydrating agents, matting agents, ultraviolet absorbers, light stabilizers, antioxidants, solvents, and the like. It may also contain resin components other than the above-mentioned component (A).

[0047] In the present invention, it is preferable to include a pigment. By including a (d1) coloring pigment (hereinafter also referred to as "component (D)") as the pigment (hereinafter also referred to as "component (d1)"), it becomes possible to express a variety of colors.

[0048] (d1) The components that can be used include chromatic pigments, white pigments, black pigments, etc. Of these, chromatic pigments are pigments that exhibit chromatic colors such as yellow, orange, red, green, blue, and purple. Examples of such chromatic pigments include inorganic ones such as ferric oxide, hydrated ferric oxide, ultramarine, cobalt blue, and cobalt green, and organic ones such as azo, naphthol, pyrazolone, anthraquinone, perylene, quinacridone, disazo, isoindolinone, benzimidazole, phthalocyanine, and quinophthalone. On the other hand, white pigments are pigments that exhibit white color, and examples include titanium dioxide, zinc oxide, and aluminum oxide. Black pigments are pigments that exhibit a black color, and examples include inorganic substances such as iron black, iron-manganese composite oxide, iron-copper-manganese composite oxide, iron-chromium-cobalt composite oxide, copper-chromium composite oxide, and copper-manganese-chromium composite oxide, as well as carbon black. These can be used individually or in combination of two or more. Furthermore, their surfaces may be treated in some way.

[0049] In the present invention, as component (D), an extender pigment (hereinafter also referred to as "component (d2)") may be mixed. Examples of component (d2) include heavy calcium carbonate, light calcium carbonate, kaolin, clay, pottery clay, china clay, diatomaceous earth, hydrated fine silica, talc, barite powder, barium sulfate, precipitated barium sulfate, barium carbonate, magnesium carbonate, silica powder, aluminum hydroxide, etc. These can be used individually or in combination of two or more. Component (d2) can be used, for example, for adjusting solid content, viscosity, gloss (such as reducing gloss), or to improve storage stability or pigment miscibility.

[0050] The mixing ratio of component (D) is preferably 1 to 300 parts by weight (more preferably 5 to 250 parts by weight) per 100 parts by weight of the solid content of component (A). Also, component (d1) is preferably 1 to 200 parts by weight (more preferably 5 to 150 parts by weight) per 100 parts by weight of the solid content of component (A). When component (d2) is used, component (d2) is preferably 100 parts by weight or less (more preferably 1 to 80 parts by weight) per 100 parts by weight of the solid content of component (A).

[0051] The coating material of the present invention can be applied mainly to buildings, civil engineering structures, etc. Examples of base materials that make up such parts include concrete, mortar, siding boards, extruded panels, ALC, gypsum boards, perlite panels, tiles, glass panels, wood panels, plastic panels, metal panels, etc. These base materials may have undergone some kind of surface treatment (filler treatment, putty treatment, surfacer treatment, sealer treatment, etc.) or may already have a coating film formed on them.

[0052] The coating material of the present invention can be diluted during painting. The above-mentioned aliphatic hydrocarbon-containing non-aqueous solvent is preferred as the diluent.

[0053] Various painting methods can be used, such as brush painting, roller painting, and spray painting. The amount of paint applied per coat is preferably 30 to 250 g / m². 2 , comfortably 50~200g / m 2 Furthermore, after the first coat of paint has dried, the next coat (overcoat) can be applied. The drying temperature is preferably -10 to 50°C, more preferably -5 to 40°C. The number of coats is preferably two or more. [Examples]

[0054] The following examples illustrate the features of the present invention. (A) Polyol compounds • (A-1) Silicone-containing acrylic polyol compound dispersion (non-aqueous dispersible resin, solids content: 50% by weight, hydroxyl value (solids content): 55KOH mg / g, silicone component content: 3% by weight (SiO2 equivalent), medium: mineral spirits) • (A-2) Acrylic polyol compound dispersion (non-aqueous dispersible resin, solids content: 50% by weight, hydroxyl value (solids content): 55KOH mg / g, medium: mineral spirits) • (A-3) Acrylic polyol compound solution (solvent-soluble resin, solids content: 50% by weight, hydroxyl value (solids content): 55KOH mg / g, medium: mineral spirits) (B) Polyisocyanate compounds (B-1) Hexamethylene diisocyanate derivative solution (solid content: 100% by weight, isocyanate group content: 12% by weight) • (B-2) Hexamethylene diisocyanate derivative solution (solid content: 100% by weight, isocyanate group content: 21% by weight) • (B-3) Hexamethylene diisocyanate derivative solution (solid content: 100% by weight, isocyanate group content: 17% by weight) (B-4) Hexamethylene diisocyanate derivative solution (solid content: 100% by weight, isocyanate group content: 14.8% by weight) Note that (B-1) is component (b1), and (B-2) to (B-4) are components (b2). (C) Silicate compound (C-1) Tetramethoxysilane • (C-2) tetramethoxysilane compound modified with i-butyl alcohol (average degree of condensation 4, transesterification rate 30%, silica retention rate 40%) (D) Pigment Rutile-type titanium dioxide (solvent) • Non-aqueous solvents containing aliphatic hydrocarbons: Mineral spirits (Additives) • Antifoaming agents, thickeners, etc.

[0055] (Example 1) • Manufacturing of the main component Main component 1 was prepared by mixing and stirring 60 parts by weight of component (A-1), 25 parts by weight of component (D), 10 parts by weight of solvent, and 5 parts by weight of additive. • Manufacturing of hardeners (B-1) Component 2.8 parts by weight, (B-2) Component 4.4 parts by weight, (C-1) Component 3 parts by weight, and solvent 9.8 parts by weight were mixed and stirred to produce curing agent 1. • Preparation of covering material Main component 1 (100 parts by weight) and hardener 1 (20 parts by weight) were mixed ([NCO] / [OH]=1.02) and stirred to obtain coating material 1.

[0056] (Examples 2-12, Comparative Examples 1-5) Except for the changes in the formulations shown in Tables 1 and 2, the main component and curing agent were prepared in the same manner as in Example 1, and the coating material was obtained by mixing them.

[0057] The coating materials prepared in Examples 1-12 and Comparative Examples 1-5 were evaluated as follows. The results are shown in Tables 1 and 2. (Stain resistance) An aluminum plate (200 mm × 120 mm × 1 mm) was coated with an epoxy primer to a dry film thickness of 30 μm and dried for 8 hours under standard conditions (temperature 23°C, relative humidity 50%) to serve as the base material. After mixing each coating material, the mixture was applied to the base material to a dry film thickness of 75 μm and dried for 7 days under standard conditions to prepare test specimen [I]. Each test specimen [I] was sprayed with a carbon dispersion (1%), dried (60°C, 1 hour), and then washed with water. The difference in brightness (ΔL value) before and after contamination of the test specimen was measured to evaluate the stain resistance test. The ΔL value was measured using a TC-1800 colorimeter (manufactured by Tokyo Denshoku Co., Ltd.). The evaluation criteria are: AA: Brightness difference (ΔL value) is less than 5 A: Brightness difference (ΔL value) is 5 or more and less than 10 B: Brightness difference (ΔL value) is between 10 and 20. C: Brightness difference (ΔL value) is 20 or more and 30 D: Brightness difference (ΔL value) is 30 or higher

[0058] (Bending resistance) Test specimens [II] were prepared by coating a tin plate (150 mm × 50 mm × 0.3 mm) with each coating material to a dry film thickness of 75 μm and drying for 7 days. All coating and drying were carried out under standard conditions. In each test specimen [II], the test plate was bent according to the method of JIS K5600-5-1 "Flexural Resistance," and its surface condition was observed. The evaluation was performed on a four-point scale (Excellent: A>B>C>D: Poor), with "A" indicating no cracking and "D" indicating cracking.

[0059] (Followability) Two slate boards measuring 100mm x 300mm x 6mm were placed side by side, and the joint between the boards (10mm wide) was filled with a modified silicone sealant (resin component: alkoxysilyl group-containing polyether polymer, plasticizer content: less than 1% by weight). This was used as the substrate for painting. Apply the coating material to the entire surface of the above substrate at a rate of 300g / m². 2 The specimens were spray-painted and dried for 7 days to form test specimen [III]. Painting and drying were all carried out under standard conditions.

[0060] Each test specimen [III] was subjected to a total of 10 cycles of repeated hot and cold testing, consisting of 18 hours of immersion in water, 3 hours of standing at -20°C, and 3 hours of standing at 50°C. After this, the appearance of the coating on each part (connecting part, plate part) was checked, and the condition of defects (blistering, peeling, cracking, etc.) was evaluated. The evaluation was performed on a four-level scale (Excellent: A>B>C>D: Poor), with "A" indicating no defects and "D" indicating clear defects.

[0061] (weather resistance) In the above-mentioned test specimen [I], after 500 hours of exposure using an accelerated weathering tester (Metal Weather; manufactured by Daipla Wintes Co., Ltd.), the changes in the appearance of the surface of test specimen [I] (gloss, color, blistering, peeling, and cracking) were observed. The evaluation was performed on a four-point scale (Excellent: A > B > C > D: Poor) by comparing the changes in appearance with the test specimen before exposure. Specimens that showed no change were rated "A", while those that showed a decrease in gloss, discoloration, blistering, peeling, or cracking were rated "D".

[0062] Table 1

[0063] Table 2

Claims

1. A coating material having a main component and a hardening agent, The main component comprises a polyol compound (A), The polyol compound (A) contains a silicone component, and the content of the silicone component in the polyol compound (A) is such that SiO2 is present in the resin solids. ２ This is equivalent to 0.1 to 20% by weight. The curing agent comprises a polyisocyanate compound (B) and a silicate compound (C). The polyisocyanate compound (B) comprises a hexamethylene diisocyanate derivative (b1) having an isocyanate group content of less than 14% by weight and a hexamethylene diisocyanate derivative (b2) having an isocyanate group content of 14% by weight or more. A coating material characterized in that the weight ratio of component (b1) to component (b2) [(b1) / (b2)] is 0.6 to 8.

2. The coating material according to claim 1, characterized in that the polyol compound (A) contains a silicone-containing polyol compound in an amount of 50 to 100% by weight on a solid content basis in component (A).

3. The coating material according to claim 1, characterized in that the polyisocyanate compound (B) contains 20 to 90% by weight of the hexamethylene diisocyanate derivative (b1).

4. The coating material according to claim 1, characterized in that the silicate compound (C) is a condensate (c1) of a tetraalkoxysilane containing an alkoxyl group having 1 to 2 carbon atoms and an alkoxyl group having 3 to 12 carbon atoms.

5. The coating material according to any one of claims 1 to 4, characterized in that it contains 0.1 to 50 parts by weight of the silicate compound (C) per 100 parts by weight of the solid content of the polyol compound (A).

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