JP2022151835A - Coating material - Google Patents

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

The present invention relates to dressings.

Conventionally, paint finish is performed to protect the frame of buildings, civil engineering structures, etc., add design, and improve aesthetics. Durable coating materials such as fluororesin, acrylic silicon resin, and polyurethane resin. are widely adopted. However, due to their durability, these durable coatings may cause problems of contamination of the coating surface. In particular, in places where a large amount of automobile exhaust gas, etc. There were cases where the paint finish that was supposed to be applied for improvement did not make sense.

On the other hand, various kinds of coating materials have been announced in which the surface of the coating is made hydrophilic and the adhered oily contaminants are removed and washed away by the action of rainwater spreading over the surface of the coating during rainfall. For example, Japanese Patent Application No. 6-506632 (International Publication No. WO94/06870) proposes mixing an organosilicate into a paint.

International publication WO94/06870

However, when organosilicate is further added to the durable coating material, although the stain resistance is improved, the formed coating tends to be hardened, and depending on the type of substrate, cracks and deterioration of conformability may occur. There was fear.

The present invention has been made in view of these points, and it is an object of the present invention to provide a coating material having sufficient stain resistance and improved crack resistance (flex resistance) and conformability. and

In order to solve such a problem, the inventors of the present invention, as a result of intensive studies, conceived of a coating material containing a specific polyisocyanate compound as an essential component, and completed the present invention.

That is, the present invention has the following features.
1. A coating material having 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) comprises a polyisocyanate compound (b1) having an isocyanate group content of less than 14% by weight and a polyisocyanate compound (b2) having an isocyanate group content of 14% by weight or more. covering material.
2. 1. The polyisocyanate compound (B) contains 20 to 95% by weight of the polyisocyanate compound (b1). The covering material described in .
3. 1. Characterized by containing 0.1 to 50 parts by weight of the silicate compound (C) with respect to 100 parts by weight of the solid content of the polyol compound (A). or 2. The covering material described in .
4. 1. The polyol compound (A) contains a silicone component. ~3. The covering material according to any one of.

According to the coating material of the present invention, it is possible to form a coating that has sufficient stain resistance and is excellent in crack resistance (bending resistance), conformability, and the like.

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

The coating material of the present invention comprises a main agent and a curing agent, the main agent comprising a polyol compound (A), and the curing agent comprising a polyisocyanate compound (B) and a silicate compound (C). .

(Main agent)
The main agent contains the polyol compound (A).

Examples of the polyol compound (A) (hereinafter also referred to as "(A) component") include polyether polyols, polyester polyols, acrylic polyols, fluorine-containing polyols, etc. In addition, phenol resin polyols, epoxy polyols, polybutadiene polyols. , polyisoprene polyols, polyester-polyether polyols, urea dispersion polyols, carbonate polyols, and the like can also be used. As the component (A), one or more of these can be used, but it is desirable to include an acrylic polyol among them.

As the acrylic polyol, a copolymer of a (meth)acrylic acid alkyl ester, a hydroxyl group-containing monomer and, if necessary, other monomers can be used. Of 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, (meth)acrylate, ) Hydroxyalkyl 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 and hydroxypentyl vinyl ether vinyl ether; hydroxyallyl ether such as ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, and the like, 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, diethylaminoethyl (meth) amino group-containing monomers such as acrylates; carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or its monoalkyl esters, itaconic acid or its monoalkyl esters, fumaric acid or its monoalkyl esters; (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, and vinyltoluene Hydrocarbon-based monomers; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, etc., and the like, and if necessary, one or more of these can be used.

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 effect of improving long-term weather resistance can be obtained. As the form of such a silicone component, a chain, branched, cyclic, or the like can be used. 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 SiO ₂ in the resin solid content. In the case of the above range, it is possible to obtain the effect of improving long-term weather resistance, and to ensure conformability to the substrate and adhesion. In the present invention, "α to β" has the same meaning as "more than or equal to α and less than or equal to β".

The SiO ₂ equivalent in the present invention is expressed in terms of the weight remaining as silica (SiO ₂ ) when firing at 900° C. after completely hydrolyzing a compound having a Si—O bond. . In general, alkoxysilanes, silicates, silicones, and the like have the property of reacting with water to cause 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 the extreme, 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 represented by the reaction formula. The SiO ₂ conversion in the present invention is obtained by converting the amount of the remaining silica component based on this reaction formula.

The method for introducing silicone into component (A) is not particularly limited and various methods can be employed.
(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 the 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 of reacting a functional group in a resin with a coupling agent having a functional group capable of reacting with the functional group, and then reacting the reactive silyl group-containing compound.

Combinations of functional groups in the above (2) and (4) include a hydroxyl group and an isocyanate group, a hydroxyl group and a carboxylic anhydride group, an amino group and an isocyanate group, a carboxyl group and an epoxy group, an amino group and an epoxy group, and an alkoxysilyl group. What should I do?

The reactive silyl groups in (3) and (4) above are those in which an alkoxyl group, a phenoxy group, a mercapto group, an amino group, a halogen, or the like is bonded to a silicon atom. As the reactive silyl group-containing compound, those having two or more reactive silyl groups in one molecule are used. Methoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, phenyltriethoxysilane Trifunctional alkoxysilanes such as methoxysilane, phenyltriethoxysilane, phenyltributoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dipropyldimethoxysilane, dipropyl Bifunctional alkoxysilanes such as diethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane; Chlorosilanes such as chlorosilane, ethyltrichlorosilane, propyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane; tetraacetoxysilane, methyltriacetoxysilane, phenyltrichlorosilane; Examples include acetoxysilanes such as acetoxysilane, dimethyldiacetoxysilane, diphenyldiacetoxysilane, and the like, and one or more of these can be used. A compound having one reactive silyl group in one molecule can also be used in combination.

The reactive silyl group-containing monomer in (3) above is a compound containing a reactive silyl group and a polymerizable double bond, such as 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., one or two of these More than one species can be used.

The coupling agent in (4) above is, for example, a compound having at least one or more alkoxysilyl groups 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 functional Silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane and the like can be mentioned, and one or more of these can be used.

In the present invention, component (A) preferably contains 50 to 100% by weight (more preferably 50 to 99% by weight, still more preferably 60 to 95% by weight) of the silicone-containing polyol compound in terms of solid content. In such a case, it is possible to obtain excellent effects on film physical properties such as weather resistance.

The hydroxyl value (solid content) of component (A) is preferably 5 to 200 KOHmg/g (more preferably 10 to 180 KOHmg/g, still more preferably 30 to 150 KOHmg/g). When the above range is satisfied, excellent effects can be exhibited in various film physical properties, stain resistance, and the like. The hydroxyl value is a value represented by the number of mg of potassium hydroxide that is equimolar to the hydroxyl groups contained in 1 g of the sample.

The glass transition temperature of component (A) is preferably -10 to 80°C (more preferably 0 to 60°C). If the glass transition point is within this range, physical properties such as stain resistance, flexibility and durability can be enhanced. The glass transition temperature is a value determined by Fox's formula based on the vinyl monomer that constitutes the resin.

Component (A) includes solvent-soluble resins, non-water-dispersible resins, and the like, and one or more of these can be used. In the present invention, it is preferable that at least a water-non-dispersible resin is included, and more preferably, a combination of a non-water-dispersible resin and a solvent-soluble resin is used. Specific aspects of the component (A) in which a non-aqueous dispersible resin and a solvent-soluble resin are used in combination include, for example,
- a non-aqueous dispersible polyol compound and a solvent-soluble polyol compound,
- a non-aqueous dispersible polyol compound and a solvent-soluble silicone-containing polyol compound,
- a non-water-dispersible silicone-containing polyol compound and a solvent-soluble polyol compound,
- a non-water-dispersible silicone-containing polyol compound and a solvent-soluble silicone-containing polyol compound,
etc. Moreover, as a polyol compound of the said aspect, the aspect containing acrylic polyol is suitable. This is advantageous in terms of stain resistance, flexibility, and the like. The non-aqueous dispersible resin is a non-aqueous solvent in which the component (A) is dispersed as resin particles. A solvent-soluble resin is a resin in which the component (A) is dissolved in a non-aqueous solvent.

The non-aqueous solvent preferably contains an aliphatic hydrocarbon-containing non-aqueous solvent (so-called weak solvent). Aliphatic hydrocarbon-containing non-aqueous solvents are less toxic than toluene, xylene, etc., are highly safe in 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 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. The aliphatic hydrocarbon content is preferably 5% by weight or more, more preferably 10 to 80% by weight, based on the total amount of the non-aqueous solvent.

The non-aqueous solvent 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.

(curing agent)
The curing agent contains (B) a polyisocyanate compound and (C) a silicate compound.

(B) 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 film. . As the component (B), those which can be crosslinked with the component (A) at room temperature are suitable. The normal temperature referred to here generally means -10° C. or higher and 50° C. or lower, preferably 5° C. or higher and 40° C. or lower.

Component (B) 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 prealphaned, biuretized, dimerized (uretidionized), 3 Examples thereof include those derivatized by quantification (isocyanurate formation), adduct formation, carbodiimidation reaction and the like, and mixtures thereof. 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. (Hereinafter, aliphatic diisocyanates and alicyclic diisocyanates are collectively referred to as "diisocyanates.")

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.

In the present invention, as the component (B), a polyisocyanate compound (b1) having an isocyanate group content in the solid content of less than 14% by weight (preferably 2% by weight or more and 13% by weight or less) and an isocyanate group content of It is characterized by containing a polyisocyanate compound (b2) of 14% by weight or more (preferably 15% by weight or more and 30% by weight or less, more preferably 16% by weight or more and 28% by weight or less). By using the above components (b1) and (b2) together, excellent effects can be exhibited in both stain resistance and flexibility. In addition, it is possible to obtain excellent conformability to the substrate, and furthermore, it is possible to obtain excellent conformability to the base material having the sealant. 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.

In the present invention, component (B) preferably contains 20 to 90% by weight (more preferably 30 to 80% by weight, still more preferably 45 to 75% by weight) of (b1). On the other hand, component (B) preferably contains 10 to 80% by weight (more preferably 20 to 70% by weight, still more preferably 25 to 55% by weight) of (b2). Further, the weight ratio [(b1)/(b2)] of the component (b1) and the component (b2) is 0.5 or more (more preferably 0.6 to 8, more preferably 0.7 to 5, 1 to 3) are particularly preferred. In the case of such a range, the above effects can be further enhanced.

The mixing ratio of component (B) may be set in consideration of 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). . With such a ratio, the effects of the present invention can be further enhanced.

The mixing ratio (weight ratio) of component (A) and component (B) is set according to 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 solid content of component (A). If the component (B) is in such a range, the above NCO/OH molar ratio can be satisfied.

The silicate compound (C) (hereinafter also referred to as "component (C)") has a function of mainly imparting hydrophilicity to the formed film. As such component (C), tetraalkoxysilanes, condensates of tetraalkoxysilanes, modified products thereof, and the like can be used. Tetraalkoxysilanes include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetrasec-butoxysilane, tetra-t-butoxysilane, tetra phenoxysilane, monoethoxytrimethoxysilane, monobutoxytrimethoxysilane, monopentoxytrimethoxysilane, monohethoxytrimethoxysilane, dimethoxydiethoxysilane, dimethoxydibutoxysilane and the like. These can be used singly or in combination of two or more.

In the present invention, 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)") is used. It is preferred to use In particular, as component (c1), alkoxyl groups having 3 to 12 carbon atoms account for 5% by weight or more and 50% by weight or less of the alkoxyl groups in the entire compound.

Examples of alkoxyl groups having 3 or more and 12 or less carbon atoms include direct chain alkoxyl 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 and t-octyloxy group; be done.

Such component (c1) can be produced by a known method. Examples of the method for producing component (c1) include a method of modifying a tetraalkoxysilane condensate having an alkoxyl group having 1 or more and 2 or less carbon atoms with an alcohol having 3 or more and 12 or less carbon atoms.

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 solid content of component (A). If the component (C) is in such a range, an excellent antifouling effect and the like can be obtained.

Further, the mixing ratio of the component (B) and the component (C) is preferably 5 to 80 parts by weight (more preferably 10 ~60 parts by weight). If the component (C) is in such a range, an excellent antifouling effect and the like can be obtained.

The curing agent of the present invention can be produced by uniformly stirring and mixing the components (B) and (C) in a conventional manner.

(Covering material)
The coating material of the present invention is a two-liquid type coating material consisting of the above main agent and the above hardening agent.
Moreover, the coating material of the present invention may contain various components in addition to the components described above in the main agent and/or the curing agent to such an extent that the effect of the present invention is not affected. Examples of such components include pigments, catalysts, plasticizers, preservatives, antifungal agents, anti-algae agents, defoaming agents, leveling agents, pigment dispersants, thickeners, anti-skinning agents, dehydrating agents, Examples include matting agents, ultraviolet absorbers, light stabilizers, antioxidants, solvents, and the like. Moreover, the resin component other than the said (A) component may be included.

In the present invention, it is preferable that a pigment is included. As the pigment (hereinafter also referred to as "(D) component"), (d1) color pigment (hereinafter also referred to as "(d1) component") is included, so that various colors can be expressed.

As the component (d1), 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.

In the present invention, (d2) an extender (hereinafter also referred to as "(d2) component") can also be mixed as the (D) component. Component (d2) includes, for example, heavy calcium carbonate, trace calcium carbonate, kaolin, clay, china clay, china clay, diatomaceous earth, hydrous fine 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 component (d2) can be used for the purposes of, for example, adjusting the solid content, adjusting the viscosity, adjusting the gloss (reducing the gloss, etc.), or improving the storage stability and pigment miscibility.

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). 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).

The coating material of the present invention can be mainly applied to buildings, civil engineering structures, and the like. Examples of base materials constituting such parts include concrete, mortar, siding board, extruded board, ALC, gypsum board, perlite board, tile, glass board, wood board, plastic board, metal board, and the like. be done. These substrates may be those subjected to some surface treatment (filler treatment, putty treatment, surfacer treatment, sealer treatment, etc.) or already coated with a coating film.

The coating material of the present invention can be diluted during application. As the diluent, the above aliphatic hydrocarbon-containing non-aqueous solvent is preferred.

As the coating method, various methods such as brush coating, roller coating, and spray coating can be employed. The amount applied during coating is preferably 30 to 250 g/m ² , more preferably 50 to 200 g/m ² per coating. Moreover, after coating is performed once and the coating film is dried, 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 coatings is preferably two or more.

Examples are shown below to further clarify the features of the present invention.
(A) Polyol compound (A-1) Silicone-containing acrylic polyol compound dispersion (non-aqueous dispersible resin, solid content: 50% by weight, hydroxyl value (solid content): 55 KOHmg/g, silicone component content: 3 weight % (as _SiO2 ), medium: mineral spirits)
- (A-2) Acrylic polyol compound dispersion (non-aqueous dispersible resin, solid content: 50% by weight, hydroxyl value (solid content): 55 KOHmg/g, medium: mineral spirit)
(A-3) Acrylic polyol compound solution (solvent-soluble resin, solid content: 50% by weight, hydroxyl value (solid content): 55 KOHmg/g, medium: mineral spirit)
(B) Polyisocyanate compound (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)
(B-1) is the component (b1), and (B-2) to (B-4) are the components (b2).
(C) Silicate compound, (C-1) tetramethoxysilane, and (C-2) i-butyl alcohol-modified tetramethoxysilane compound (average condensation degree 4, transesterification rate 30%, residual silica ratio 40%)
(D) Pigment/rutile titanium oxide
(solvent)
・Non-aqueous solvent containing aliphatic hydrocarbon: Mineral spirit (additive)
・Antifoaming agents, thickeners, etc.

(Example 1)
Manufacture of main agent 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 were mixed and stirred to produce main agent 1.
・Production of curing agent 2.8 parts by weight of component (B-1), 4.4 parts by weight of component (B-2), 3 parts by weight of component (C-1) and 9.8 parts by weight of solvent are mixed and stirred. Hardener 1 was prepared.
-Preparation of Coating Material Main component 1 (100 parts by weight) and curing agent 1 (20 parts by weight) were mixed ([NCO]/[OH]=1.02) and stirred to obtain a coating material 1.

(Examples 2-12, Comparative Examples 1-5)
A main agent and a curing agent were prepared in the same manner as in Example 1 except that the formulations were changed to those shown in Tables 1 and 2, and mixed to obtain a coating material.

The following evaluations were performed on the dressings prepared in Examples 1 to 12 and Comparative Examples 1 to 5 above. 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-based undercoat material so that the dry film thickness was 30 μm, and dried for 8 hours under standard conditions (temperature 23 ° C., relative humidity 50%). material. After each coating material was mixed with the base material, the mixture was coated so as to have a dry film thickness of 75 μm and dried under standard conditions for 7 days to prepare a specimen [I].
A carbon dispersion (1%) was sprayed on each specimen [I], dried (60° C., 1 hour), and then washed with water. The lightness difference (ΔL value) of the specimen before and after contamination was measured to evaluate the contamination resistance test. The ΔL value was measured using a TC-1800 color difference meter (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 10 or more and less than 20 C: Brightness difference (ΔL value) is 20 or more and 30
D: Brightness difference (ΔL value) of 30 or more

(Flexibility)
Each coating material was applied to a tin plate (150 mm×50 mm×0.3 mm) so that the dry film thickness was 75 μm, and dried for 7 days to prepare a specimen [II]. All coating and drying were performed under standard conditions.
For each test piece [II], the surface condition was observed after bending the test plate according to the method of JIS K5600-5-1 “flex resistance”. The evaluation was performed in four grades (excellent: A>B>C>D: inferior), with "A" indicating no cracks and "D" indicating cracks.

(Followability)
Two slate plates of 100 mm × 300 mm × 6 mm are installed side by side, and a modified silicone sealant (resin component: alkoxysilyl group-containing polyether polymer, plasticizer content: 1 wt% less than) was used as the base material to be painted.
A coating material was spray-coated on the entire surface of the base material at a coating amount of 300 g/m ² , dried for 7 days, and used as test sample [III]. All coating and drying were performed under standard conditions.

Each test piece [III] was immersed in water for 18 hours, left at -20 ° C. for 3 hours, and left at 50 ° C. for 3 hours. Part) was checked for the appearance of the film, and the state of occurrence of defects (swelling, peeling, cracking, etc.) was evaluated. The evaluation was made on a 4-point scale (excellent: A>B>C>D: inferior), with "A" indicating that no defects were observed and "D" indicating that defects were clearly observed.

(Weatherability)
After exposing the test sample [I] to an accelerated weathering tester (Metal Weather; manufactured by Daipla Wintes Co., Ltd.) for 500 hours, changes in the appearance of the test sample [I] surface (gloss, color, floating, peeling) and cracks) were observed. For the evaluation, the change in appearance is compared with the specimen before exposure, and "A" is given when no change is observed, and "D" is given when loss of gloss, discoloration, lifting, peeling or cracking occurs. It was performed in four stages (excellent: A>B>C>D: inferior).

Claims (4)

A coating material having 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) comprises a polyisocyanate compound (b1) having an isocyanate group content of less than 14% by weight and a polyisocyanate compound (b2) having an isocyanate group content of 14% by weight or more. covering material. 2. The coating material according to claim 1, wherein the polyisocyanate compound (B) contains 20 to 90% by weight of the polyisocyanate compound (b1). 3. The covering material according to claim 1, comprising 0.1 to 50 parts by weight of the silicate compound (C) with respect to 100 parts by weight of the solid content of the polyol compound (A). The coating material according to any one of claims 1 to 3, wherein the polyol compound (A) contains a silicone component.