JP2024040192A - Covering material set - Google Patents

Abstract

[Problem] To provide a coating material that makes use of the design properties of a patterned coating while suppressing the progression of deterioration such as discoloration and cracking caused by the patterned coating, and can maintain its aesthetic appearance for a long period of time. [Solution] The present invention is a coating material set for forming a transparent laminated coating, the coating material set comprising at least a first coating material and a second coating material, the first coating material and the second coating material each containing a (meth)acrylic acid alkyl ester (A) having a specific alkyl group with 3 or more carbon atoms as a resin constituent, using a binder containing an inorganic component derived from a silicon compound, and forming a coating with a visible light transmittance of 30% or more. [Selected Figure] None

Description

The present invention relates to a novel dressing set.

Conventionally, in the exterior of buildings and civil engineering structures, coatings have been formed on various base materials using various coating materials for the purpose of protecting the base materials, imparting color to the base materials, and the like. From the viewpoint of aesthetics, etc., such a coating surface may be provided with a pattern such as an uneven pattern or a multicolored pattern.

However, when such a patterned coating surface is exposed outdoors for a long period of time, it tends to deteriorate due to the effects of sunlight, rain, etc. Specifically, discoloration, cracking, etc. may occur. Therefore, it becomes necessary to apply a transparent coating agent to the pattern coating surface where such deterioration is likely to occur (for example, Patent Document 1, etc.).

Japanese Patent Application Publication No. 2001-227138

By the way, among the above-mentioned patterned coating surfaces, for example, those having an uneven pattern, the way sunlight hits the surface, the way water flows, the degree of retention, etc. may differ depending on the uneven shape etc. becomes. Therefore, in areas where the load from sunlight or water is large, deterioration tends to progress more easily, and local discoloration, cracking, etc. may occur. Furthermore, in the case where the coating surface has a multicolored pattern and there is a difference in durability depending on the color tone, similar deterioration may occur in the region of the color tone where the durability is relatively insufficient.

Even if such a patterned coating surface is painted using a transparent coating agent such as that described in the above patent document, the progress of deterioration of the patterned coating surface cannot be sufficiently suppressed, and the coating cannot be applied. It may be difficult to obtain the desired effect.

The present invention has been developed in view of these problems, and it is possible to suppress the progress of deterioration such as discoloration and cracking caused by the patterned coating, and to maintain its aesthetic appearance for a long period of time while taking advantage of the design of the patterned coating. The purpose is to provide a covering material that can be used.

In order to solve these problems, the inventors of the present invention have conducted intensive studies and have come up with a dressing material set consisting of at least two types of specific covering materials, and have completed the present invention.

That is, the present invention has the following features.
1. A coating material set for forming a transparent laminated film,
The covering material set includes at least a first covering material and a second covering material,
The first covering material and the second covering material are each
(meth)acrylic acid alkyl ester (A) having an alkyl group having 3 or more carbon atoms selected from cyclohexyl methacrylate and 2-ethylhexyl acrylate , and methyl methacrylate as resin constituents,
selected from reactive silyl group-containing monomers, reactive silyl group-containing mercapto compounds, silane coupling agents, tetrafunctional alkoxysilane compounds, trifunctional alkoxysilane compounds, bifunctional alkoxysilane compounds, siloxane compounds, or polycondensates thereof A binder containing an inorganic component derived from one or more silicon compounds ,
The above component (A) contains 2-ethylhexyl acrylate (a1),
The ratio of cyclohexyl methacrylate in the resin constituent components is 20 to 46% by weight, the ratio of 2-ethylhexyl acrylate is 4 to 52% by weight, and the ratio of methyl methacrylate is 23 to 55% by weight,
If the weight ratio of the component (a1) in the component (A) is r,
r (r ₁ ) in the binding material of the first covering material is larger than r (r ₂ ) in the binding material of the second covering material ,
The first coating material and the second coating material each form a coating having a visible light transmittance of 30% or more.
A covering material set characterized by:
2. 1. The first coating material and the second coating material each form a coating having an ultraviolet transmittance of 30% or less. Covering set as described.
3. If the weight ratio of the inorganic content to the nonvolatile content of the binder is s, then
s (s ₁ ) in the binding material of the first covering material is larger than s (s ₂ ) in the binding material of the second covering material 1. or 2. Covering material set as described in .
(However, the weight ratio s of the inorganic content to the nonvolatile content of the binder is a value calculated using the following formula.
[Formula] s (weight %) = {Weight of inorganic components contained in the binder} / {Weight of non-volatile components of the binder} x 100
(The "weight of non-volatile content of the binder" and the "weight of inorganic content contained in the binder" are measured according to the method of JIS K 5601-1-2 "Heating residue". "Weight of inorganic components contained in the binder" is the value measured at a heating temperature of 135°C and a heating time of 60 minutes. This is the value when measured under the following conditions.))
4. If the weight ratio of the inorganic content to the nonvolatile content of the binder is s, then
s (s ₁ ) in the binder of the first covering material is 0.1 to 20% by weight, and s (s ₂ ) in the binder of the second covering material is 0.01 to 10% by weight. 1. ~3. A set of covering materials as described in any of the above.
5. 1. The first coating material is an undercoat material, and the second coating material is a topcoat material. ~4. A set of covering materials as described in any of the above.

According to the present invention, while taking advantage of the design of the patterned coating, it is possible to suppress the progress of deterioration such as discoloration and cracking caused by the patterned coating, and maintain the aesthetic appearance for a long period of time.

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

The present invention relates to a coating material set for forming a transparent laminated film. The coating material set of the present invention consists of at least a first coating material and a second coating material, both of which contain, as a binder, a (meth)acrylic acid alkyl ester (A) having an alkyl group having 3 or more carbon atoms ( Component (A) contains an alkyl (meth)acrylate having an alkyl main chain having 3 or more carbon atoms. Contains ester (a1) (hereinafter also referred to as "component (a1)"). First, common features of the first covering material and the second covering material (hereinafter, both may be collectively referred to simply as "covering material") will be described.

The coating material in the present invention contains a resin component as a binding material, and the resin component contains (meth)acrylic acid alkyl ester (A) having an alkyl group having 3 or more carbon atoms as a resin constituent component. Such a resin component can mainly be provided with resistance to water by the component (A). In the present invention, acrylic acid alkyl ester and methacrylic acid alkyl ester are collectively referred to as (meth)acrylic acid alkyl ester.

Examples of the form of the alkyl group in component (A) include linear, branched, and cyclic. Component (A) includes, for example, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, t-pentyl (meth)acrylate, 1-ethylpropyl (meth)acrylate, 2-methylbutyl (meth)acrylate , 3-methylbutyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, 2-methylpentyl (meth)acrylate, (meth)acrylic acid 4-Methylpentyl, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, (meth)acrylate ) n-decyl acrylate, n-undecyl (meth)acrylate, n-lauryl (meth)acrylate, and the like. These can be used alone or in combination of two or more. Among these, as component (A), those having an alkyl group having 4 or more carbon atoms (more preferably 4 to 10 carbon atoms, still more preferably 6 to 8 carbon atoms) are preferable.

The proportion of component (A) in the resin constituent components is 20% by weight or more, preferably 25 to 99% by weight, more preferably 30 to 98% by weight. When the component (A) is in the above ratio, resistance to water, etc. can be improved, and effects such as suppressing deterioration such as discoloration and cracking, and maintaining aesthetic appearance can be obtained. In the present invention, "α to β" is synonymous with "above α and below β".

In the coating material of the present invention, (meth)acrylic acid alkyl ester (a1) having an alkyl main chain having 3 or more carbon atoms (hereinafter also referred to as "component (a1)") is used as component (A) in the resin constituent components. include. In such a component (a1), the alkyl moiety is a linear or branched alkyl group (excluding cyclic ones), and the main chain (longest straight carbon chain) has 3 or more carbon atoms. Something can be used. By including the component (a1) in the resin component, in addition to water resistance, crack prevention properties can be further improved, which is more suitable in terms of water-blocking properties, maintaining aesthetic appearance, extending the life of the base material, and the like.

Component (a1) has an alkyl main chain having 3 or more carbon atoms in the alkyl moiety. The alkyl moiety of component (a1) may have various side chains (for example, an alkyl group having fewer carbon atoms than the alkyl main chain) as long as it has such an alkyl main chain. As component (a1), among the above-mentioned components (A), those satisfying such conditions can be used, such as n-propyl (meth)acrylate, isobutyl (meth)acrylate, and (meth)acrylate. 1-ethylpropyl, t-pentyl (meth)acrylate, neopentyl (meth)acrylate, n-butyl (meth)acrylate, 2-methylbutyl (meth)acrylate, isopentyl (meth)acrylate, (meth)acrylate 3-methylbutyl acid, 2-ethylbutyl (meth)acrylate, n-pentyl (meth)acrylate, 2-methylpentyl (meth)acrylate, 4-methylpentyl (meth)acrylate, n-(meth)acrylate hexyl, 2-ethylhexyl (meth)acrylate, n-heptyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, (meth)acrylic acid Examples include n-decyl, n-undecyl (meth)acrylate, and n-lauryl (meth)acrylate. These can be used alone or in combination of two or more. Among these, as component (a1), those having an alkyl main chain having 4 or more carbon atoms (more preferably 4 to 10, still more preferably 6 to 8) in the alkyl moiety are suitable.

Examples of component (A) other than (a1) (hereinafter also referred to as "component (a2)") include isopropyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, etc. It will be done. These can be used alone or in combination of two or more.

The weight ratio of component (a1) in component (A) can be expressed as "r". This "r" is a value calculated using the following formula.
[Formula] r = {weight of component (a1) in resin component}/{weight of component (A) in resin component}

In addition to the above-mentioned (A) component, the resin constituent components can include other monomers (hereinafter also referred to as "(B) component") other than the above-mentioned (A) component. Component (B) is, for example, methyl (meth)acrylate, ethyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, or a carboxyl group-containing monomer, an amino group-containing monomer, or a pyridine monomer. , hydroxyl group-containing monomer, nitrile group-containing monomer, amide group-containing monomer, epoxy group-containing monomer, carbonyl group-containing monomer, sulfonic acid group-containing monomer, alkoxysilyl group-containing monomer, fluorine-containing monomer, aromatic monomer, polyoxyalkylene chain-containing monomer Examples include monomers, divinyl monomers, trivinyl monomers, ultraviolet absorbing group-containing monomers, photostable group-containing monomers, and the like. These can be used alone or in combination of two or more. The composition ratio of component (B) is preferably 80% by weight or less (more preferably 1 to 75% by weight, more preferably 2% by weight) in the resin components {in the total amount of components (A) and (B)}. ~70% by weight). In addition, in this invention, a monomer is a compound which has a polymerizable unsaturated double bond.

In the present invention, an embodiment containing a monomer containing an ultraviolet absorbing group and/or a monomer containing a photostable group as the component (B) is preferable in terms of improving the effects of the present invention. The ultraviolet absorbing group-containing monomer is a compound having an ultraviolet absorbing group and a polymerizable unsaturated double bond, and examples of the ultraviolet absorbing group include a benzophenone ultraviolet absorbing group, a benzotriazole ultraviolet absorbing group, Examples include triazine-based ultraviolet absorbing groups and salicylate-based ultraviolet absorbing groups. The photostable group-containing monomer is a compound having a photostable group and a polymerizable unsaturated double bond, and examples of the photostable group include a piperidyl group.

Such a resin component can be produced, for example, by polymerizing component (A) (preferably containing component (a1)) and, if necessary, a monomer group containing component (B). Examples of the form of the resin component include water-soluble resins, water-dispersible resins, solvent-soluble resins, solvent-free resins, non-aqueous dispersible resins, and composites thereof. Among these, the water-dispersible resin (resin emulsion) can be produced by a one-stage to multi-stage (two-stage, three-stage or more) emulsion polymerization method. These may have crosslinking reactivity, and may be either one-part type, two-part type, or the like.

It is desirable that the binder in the first coating material and the second coating material contain an inorganic component. Such an inorganic component is derived from the inorganic compound that constitutes the binder, and contributes to suppressing the progress of deterioration caused by the patterned coating, improving adhesion to the patterned coating surface, etc., and enhancing the effects of the present invention. It is something.

Examples of such inorganic compounds include silicon compounds, aluminum compounds, titanium compounds, and zirconium compounds. These can be used alone or in combination of two or more. In the present invention, it is desirable to include a silicon compound as the inorganic compound.

Examples of silicon compounds include reactive silyl group-containing monomers, reactive silyl group-containing mercapto compounds, silane coupling agents, alkoxysilane compounds (tetrafunctional alkoxysilane compounds, trifunctional alkoxysilane compounds, bifunctional alkoxysilane compounds, etc.) , siloxane compounds, or polycondensates thereof. These can be used alone or in combination of two or more. The reactive silyl group is one in which one or more functional groups selected from, for example, an alkoxyl group, a phenoxy group, a hydroxyl group, a mercapto group, an amino group, an acetoxy group, an oxime group, an amide group, a halogen group, etc. are bonded to a silicon atom. It is. As such a reactive silyl group, one in which one or more functional groups selected from an alkoxyl group and a hydroxyl group are bonded to a silicon atom is particularly suitable.

The reactive silyl group-containing monomer is a compound having a reactive silyl group and an ethylenically unsaturated 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)acryloyloxypropyltrimethoxysilane, ) Acryloyloxypropyltriethoxysilane, γ-(meth)acryloyloxypropylmethyldimethoxysilane, vinylmethyldimethoxysilane, methyldimethoxysilylethyl vinyl ether, methyldimethoxysilylpropyl vinyl ether, and the like.

The reactive silyl group-containing mercapto compound is a compound having a reactive silyl group and a mercapto group, such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, -Mercaptopropylmethyldiethoxysilane, 3-mercaptopropyldimethylmethoxysilane, 3-mercaptopropyldimethylethoxysilane, 3-mercaptopropyltriacetoxysilane, 3-mercaptopropylmethyldiacetoxysilane, 3-mercaptopropyldimethylacetoxysilane, 3 -Mercaptopropyltrioxime silane and the like.

The silane coupling agent is, for example, a compound having at least one reactive silyl group and other functional group in one molecule, such as 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane. Isocyanate group-containing silane compounds such as tris-(trimethoxysilylpropyl)isocyanurate; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxy Epoxy group-containing silane compounds such as silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, polymer-type polyfunctional epoxysilane; 3-triethoxysilylpropylsuccinic anhydride, 3-triethoxysilane Acid anhydride groups such as methoxysilylpropylsuccinic anhydride, 3-methyldimethoxysilylpropylsuccinic anhydride, methyldiethoxysilylpropylsuccinic anhydride, 1-carboxy-3-triethoxysilylpropylsuccinic anhydride ( carboxyl group)-containing silane compound; N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3 - Amino group-containing silane compounds such as aminopropyltriethoxysilane and 3-aminopropylmethyldimethoxysilane; 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, 3-trimethoxysilyl-N- Ketoimino group-containing silane compounds such as (1,3-dimethyl-butylidene)propylamine; and the like.

Examples of alkoxysilane compounds include tetraethoxysilane, tetramethoxysilane, tetran-propoxysilane, tetraisopropoxysilane, tetraisobutoxysilane, tetrasec-butoxysilane, tetrat-butoxysilane, and tetraphenoxysilane. Functional alkoxysilane compounds; methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, Propyltriethoxysilane, propyltripropoxysilane, propyltributoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, butyltributoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, Trifunctional alkoxysilane compounds such as trifluoropropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxy Silane, diethyldibutoxysilane, diethyldipropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, dimethoxymethylphenylsilane , bifunctional alkoxysilane compounds such as methylphenyldiethoxysilane; and the like.

Examples of the siloxane compound include cyclic siloxane compounds, linear siloxane compounds, and branched siloxane compounds. Among these, examples of the cyclic siloxane compound include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like.

Such an inorganic compound only needs to be included in the coating material at the time of application; for example, it can be introduced during or after the polymerization of the resin component, during the production of the coating material, during the formulation of the coating material, etc. . Specifically, for silicon compounds, for example, a reactive silyl group-containing monomer can be used as the component (B) during the polymerization of the resin component, and a reactive silyl group-containing monomer can be used as a chain transfer agent during the polymerization of the resin component. Mercapto compounds containing silyl groups can be used. In addition, silane coupling agents, tetrafunctional alkoxysilane compounds, trifunctional alkoxysilane compounds, bifunctional alkoxysilane compounds, siloxane compounds, etc., or polycondensates thereof, may be used, for example, during polymerization of resin components or after polymerization. It can be mixed with the resin component of , mixed at the time of manufacturing the covering material, or mixed at the time of preparing the covering material.

The weight ratio of the inorganic content to the nonvolatile content of the binder can be expressed as "s". This "s" is a value calculated using the following formula.
[Formula] s (weight %) = {Weight of inorganic components contained in the binder} / {Weight of non-volatile components of the binder} x 100

Here, the "weight of non-volatile content of the binder" and the "weight of inorganic content contained in the binder" can be measured according to the method of JIS K5601-1-2 "Heating residue". "Weight of non-volatile components of the binder" is a value measured at a heating temperature of 135°C and a heating time of 60 minutes. "Weight of inorganic components contained in the binder" is a value measured at a heating temperature of 550°C and a heating time of 60 minutes. This value was measured under the condition of heating time of 180 minutes.

The first coating material and the second coating material in the present invention both form a transparent film, that is, a film that transmits visible light. This makes it possible to form a transparent laminated film, and to obtain a finish that takes advantage of the design of the patterned film surface. The transparency is sufficient as long as the surface of the pattern coating can be visually recognized, and the coating may be colorless and transparent, colored transparent, or glossy or matte (7 minutes gloss, 5 minutes gloss, 3 minutes gloss). etc.) may be used. A colored transparent film can be formed using a coating material containing a colored pigment, dye, etc., for example. The matte film can be formed by, for example, a coating material containing an extender pigment, a matte agent, and the like.

The degree of visible light transmittance can be indicated by visible light transmittance. The visible light transmittance is preferably 30% or more, more preferably 35 to 100%, and even more preferably 40 to 95%. In addition, the visible light transmittance is the value measured using a spectrophotometer for the transmittance of light at a wavelength of 580 nm for a film with a thickness of 30 μm (transmittance is 100% in the case of no film (air)). be.

In order to obtain such visible light transmittance, for example, the proportion of colored pigment in the coating material may be set low. The proportion of colored pigment in the coating material is preferably 10% by weight or less, more preferably 5% by weight or less, even more preferably 0 to 3% by weight. Embodiments in which the coating material does not contain colored pigments are also suitable.

The coating material used in the present invention is preferably one that forms a film having an ultraviolet transmittance of 30% or less (more preferably 20% or less, still more preferably 0 to 15%). In the present invention, when the ultraviolet transmittance is within the above range, resistance to sunlight can be increased, and effects such as suppressing deterioration such as discoloration and cracking and maintaining aesthetic appearance can be obtained. In addition, the ultraviolet transmittance is the value measured by using a spectrophotometer to measure the transmittance of light at a wavelength of 350 nm for a film with a thickness of 30 μm (transmittance is 100% in the case of no film (air)). .

As means for obtaining such ultraviolet transmittance, for example,
(1) A coating material containing a resin component having an ultraviolet absorbing group is used.
(2) Use a coating material containing an ultraviolet absorber.
(3) Use a coating material containing ultraviolet-shielding powder.
etc. These means may be employed singly or in combination.

In the above (1), for example, a resin component containing an ultraviolet absorbing group-containing monomer may be used as the component (B). The proportion of the ultraviolet absorbing group-containing monomer in the resin component is preferably 0.05 to 10% by weight, more preferably 0.1 to 5% by weight.

Examples of the ultraviolet absorber in (2) above (excluding compounds having a polymerizable unsaturated double bond) include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, and salicylate ultraviolet absorbers. UV absorbers, cyanoacrylate-based UV absorbers, benzoate-based UV absorbers, malonic acid ester-based UV absorbers, oxalic acid anilide-based UV absorbers, and the like. Among these, examples of benzophenone ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and 2-hydroxy-4-n -Octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2'-dihydroxy -4-methoxybenzophenone, 2,2'-dihydroxy-4,4'dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4- Examples include methoxy-2'-carboxybenzophenone and 2-hydroxy-4-stearyloxybenzophenone. Examples of benzotriazole ultraviolet absorbers include 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 3-(2H-benzotriazol-2-yl)-5-(1,1 -dimethylethyl)-4-hydroxyalkyl ester, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl) -yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(2H-benzotriazol-2-yl) Examples include reaction products of -5-t-butyl-4-hydroxyphenyl)propionate and polyethylene glycol. Examples of triazine-based ultraviolet absorbers include 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hydroxyphenyl derivatives, 2-(2 ,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester reaction product, 2,4-bis' Examples include 2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3-5-triazine.These can be used alone or in combination of two or more.Ultraviolet absorber The mixing ratio is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the resin component.

As the ultraviolet shielding powder in (3) above, those having the ability to absorb and/or reflect ultraviolet rays can be used, such as alumina, zirconium oxide, barium sulfate, precipitated barium sulfate, calcium carbonate, magnesium carbonate, Aluminum hydroxide, magnesium hydroxide, titanium oxide, magnesium oxide, zinc oxide, boron nitride, bismuth oxychloride, zinc phosphate, mica, agarite, talc, diatomaceous earth, white clay, kaolin, clay, china clay, barite powder, silica sand, Examples include silica powder, white carbon, metal powder, and organic resin powder. These can be used alone or in combination of two or more. The average particle diameter of the ultraviolet shielding powder is preferably 1 to 200 nm. In (3) above, it is desirable to set the mixing ratio of the ultraviolet shielding powder within a range that can ensure visible light transparency.

In addition to the above-mentioned components, the coating material of the present invention may contain known additives, such as aggregate, colored grains, colored pigments, extender pigments, dyes, and gloss, if necessary, within a range that does not significantly impede the effects of the present invention. Eraser, thickener, wetting agent, antifreeze agent, film forming aid, preservative, antifungal agent, antialgae agent, antibacterial agent, dispersant, antifoaming agent, light stabilizer, antioxidant, adhesion It may contain a imparting agent, a stain-reducing agent, a hydrophilic agent, a water repellent, a crosslinking agent, a curing accelerator, a catalyst, and the like. Examples of the form of the coating material include a one-component type, a two-component type (form consisting of a base agent and a curing agent), a multi-component type containing three or more components, and the like. In two-component or multi-component coating materials, the base agent, curing agent, etc. can be mixed at the time of applying the coating material (immediately before application).

In the present invention, bonding materials having different ratios r of the component (a1) to the component (A) are used in the first coating material and the second coating material. That is, r in the binding material of the first covering material (hereinafter also referred to as "r ₁ ") is larger than r in the binding material of the second covering material (hereinafter also referred to as "r ₂ "), and r ₁ - r ₂ >0 is satisfied. In the present invention, by using a combination of the first coating material and the second coating material containing the binder in this embodiment, it is possible to sufficiently suppress the progress of deterioration such as discoloration and cracking caused by the patterned coating surface. This also improves the adhesion to the patterned coating surface. Furthermore, effects such as maintaining aesthetic appearance and extending the life of the base material can be enhanced. Note that r ₁ and r ₂ are values calculated by the following formula 1 and the following formula 2, respectively.
[Formula 1] r ₁ = {weight of component (a1) in the resin components in the first coating material}/{weight of component (A) in the resin components in the first coating material}
[Formula 2] r ₂ = {weight of component (a1) in the resin components in the second coating material}/{weight of component (A) in the resin components in the second coating material}

r ₁ represented by the above formula is preferably 0.1 to 1.0, more preferably 0.2 to 0.9, even more preferably 0.3 to 0.85, particularly preferably 0.4 to 0. 8, and r ₂ is preferably 0.05 to 0.8, more preferably 0.1 to 0.6, even more preferably 0.15 to 0.55, particularly preferably 0.2 to 0.5. It is. The difference between r ₁ and r ₂ (r ₁ - r ₂ ) is preferably 0.01 or more, more preferably 0.05 to 0.9, even more preferably 0.08 to 0.8, particularly preferably 0. .1 to 0.7. In such a case, it becomes possible to fully obtain the above-mentioned effects.

In the present invention, the first coating material and the second coating material can use binders having different weight ratios of inorganic components to nonvolatile components of the binder. In this case, it is desirable that s (hereinafter also referred to as "s ₁ ") in the binding material of the first covering material be larger than s (hereinafter also referred to as "s ₂ ") in the binding material of the second covering material. That is, it is desirable to satisfy s ₁ −s ₂ >0. By using a combination of the first coating material and the second coating material containing the binder in this manner, it is possible to sufficiently suppress the progress of deterioration such as discoloration and cracking caused by the patterned coating surface, and the patterned coating Adhesion to surfaces is also improved. Furthermore, effects such as maintaining aesthetic appearance and extending the life of the base material can be enhanced. Note that s ₁ and s ₂ are values calculated using Equation 3 below and Equation 4 below, respectively.
[Formula 3] s ₁ (wt%) = {Weight of inorganic components contained in the binder in the first coating material}/{Weight of non-volatile components of the binder in the first coating material}×100
[Formula 4] s ₂ (weight %) = {weight of inorganic components contained in the binder in the second coating material} / {weight of non-volatile components of the binder in the second coating material}×100

s ₁ represented by the above formula is preferably 0.1 to 20% by weight, more preferably 1 to 15% by weight, even more preferably 2 to 10% by weight, and s ₂ is preferably 0.01 to 10% by weight. % by weight, more preferably 0.03 to 3% by weight, even more preferably 0.05 to 2% by weight. The difference between s ₁ and s ₂ (s ₁ −s ₂ ) is preferably 0.1 to 20% by weight, more preferably 1 to 15% by weight. In such a case, it becomes possible to fully obtain the above-mentioned effects.

In the present invention, as the binder of the first coating material, a resin component containing an epoxy group-containing monomer as the component (A) and the component (B) can be used. By using such a resin component in the first covering material, the adhesion to the patterned coating surface is increased, and the effects of the present invention can be improved.

Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, diglycidyl fumarate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxyvinylcyclohexane, allyl glycidyl ether, and ε-caprolactone-modified glycidyl (meth)acrylate. ) acrylate, β-methylglycidyl (meth)acrylate, and the like. These can be used alone or in combination of two or more.

The proportion of the epoxy group-containing monomer in the resin component is preferably 0.1 to 20% by weight (more preferably 0.5 to 15% by weight). Within this range, a sufficient effect of improving adhesion can be obtained, and the effects of the present invention can be improved.

The covering material set of the present invention includes the first covering material and the second covering material as described above. The dressing set of the present invention is composed of at least one type of first covering material and at least one type of second covering material, and examples of the combination include, for example, one type of first covering material and one type of second covering material. A combination with a second coating material, a combination of two or more types of first coating materials and one type of second coating material, a combination of one type of first coating material and two or more types of second coating materials, two types Examples include a combination of the above-described first covering material and two or more types of second covering materials. When using two or more kinds of covering materials in the first covering material or the second covering material, for example, two or more kinds having different colors and gloss levels can be combined. Specifically, for example, a combination of a colorless transparent first coating material and a colorless transparent second coating material, a combination of a colorless transparent first coating material and a colored transparent second coating material, a colored transparent first coating material, etc. A combination of a coating material and a colorless transparent second coating material, a combination of a colorless transparent first coating material, a colored transparent second coating material and a colorless transparent second coating material, a colorless transparent first coating material and a colored A combination of a transparent first coating material and a colorless transparent second coating material, a combination of a glossy first coating material and a glossy second coating material, a glossy first coating material and a matte type Combination with second coating material, combination of matte first coating material and glossy second coating material, combination of glossy first coating material, glossy second coating material and matte second coating material Examples include a combination of a glossy first coating material, a matte first coating material, and a matte second coating material.

In the present invention, a transparent laminated film can be formed by applying (painting) such a first covering material and a second covering material to a patterned film surface. That is, a transparent laminated film can be formed by sequentially applying the first coating material and the second coating material to the patterned coating surface, where the first coating material is the base coating material and the second coating material is the base coating material. Can be used as a top coat material. In the present invention, it is desirable to apply the first coating material, dry the film, and then apply the second coating material.

In the present invention, the above-mentioned coating materials (first coating material and second coating material) are applied to a patterned coating surface (for example, a patterned coating surface having an uneven pattern and/or a multicolored pattern) provided on a base material. Can be applied to form a new coating.

Even if such a pattern coating surface is painted with a conventional transparent coating agent, it is difficult to suppress the progress of discoloration and cracking in areas that are naturally prone to deterioration. There is also a risk that minute cracks that occur on the surface will progress over time. Such cracks tend to spread to the transparent coating on the patterned coating surface, which impairs the aesthetics, water-blocking properties, etc. of the transparent coating, and makes it impossible to obtain sufficient effects in terms of extending the life of the base material. It becomes difficult.

In contrast, the present invention makes use of the design properties of the patterned coating surface (e.g. uneven patterns, multicolored patterns, etc.), suppresses the progress of deterioration such as discoloration and cracking caused by the patterned coating surface, and maintains a beautiful appearance for a long period of time. It is possible to maintain the properties of the base material, and it is also possible to extend the life of the base material. It is thought that such an effect is produced because the laminated film newly installed by coating with the coating material set of the present invention exhibits sufficient resistance to sunlight and water.

Examples of patterned coating surfaces include those formed on the surface of base materials such as buildings and civil engineering structures, especially those formed on exterior surfaces (exterior walls, roofs, etc.) that are easily affected by sunlight and water. It is preferable that the Examples of the base material include concrete, mortar, and plate-shaped base materials. Among these, examples of plate-like base materials include cement boards, extruded boards, slate boards, PC boards, ALC boards, fiber-reinforced cement boards, metal siding boards, ceramic siding boards, ceramic boards, calcium silicate boards, Examples include plastic board, hard wood cement board, PVC extrusion siding board, and plywood. The present invention is particularly useful when the base material is a plate-like base material.

When the pattern coating surface is composed of a plurality of plate-shaped base materials, the joints between the plate-shaped base materials may be filled with a joint material such as a sealant or a dry joint material. Among these, examples of sealants include silicone sealants, modified silicone sealants, polysulfide sealants, modified polysulfide sealants, acrylic urethane sealants, polyurethane sealants, SBR sealants, and butyl rubber sealants. Examples include wood.

The patterned coating surface may have, for example, an uneven pattern and/or a multicolored pattern. Such a patterned film is formed using one or more types of coating agents. Various coating agents can be used, such as colored or uncolored, opaque or transparent, such as organic binders such as vinyl acetate resin, polyester resin, alkyd resin, epoxy resin, acrylic resin, urethane resin, etc. Examples include inorganic binders such as silicone resins, alkoxysilanes, colloidal silica, and silicates, and organic-inorganic composite binders such as acrylic silicone resins. The patterned coating surface is a coating of one layer or two or more layers, and may be a layered layer of colored coating layers, transparent coating layers, etc., for example.

There are various types of uneven patterns, such as tile-like patterns, brick-like patterns, stone-like patterns, rock-like patterns, wood-like patterns, geometric patterns, striped patterns, lattice patterns, polka dot patterns, and sand wall patterns. , yuzu skin pattern, ripple pattern, etc., as well as graphic patterns with designs of animals and plants. Specifically, the shape of the convex portion when the concave-convex pattern is viewed from the front includes, for example, a square, a rectangle, a circle, an ellipse, a triangle, a rhombus, a polygon, an irregular shape, and the like. Further, the cross-sectional shape of the convex portion in the uneven pattern includes, for example, a trapezoid, square, rectangle, semicircle, waveform, step shape, triangle, chevron, irregular shape, and the like. The recesses in the uneven pattern may be flat and form joints. The height difference between the concave portion and the convex portion may be constant or different in each region, but is preferably 20 mm or less, and more preferably about 1 to 15 mm. Such a concavo-convex pattern may be provided on either or both of the base material and the patterned coating.

A multicolor pattern is a pattern in which at least two or more colors are visibly mixed, such as a pattern in which spots of two or more colors are mixed, or spots (one or more colors) scattered on a background color. patterns, patterns painted in two or more colors (for example, island patterns, linear patterns, tile-like patterns, brick-like patterns, stone-like patterns, rock-like patterns, wood-like patterns, geometric patterns, stripes) pattern, lattice pattern, random pattern, etc.). Such a multicolored pattern may be formed, for example, by various printing methods (inkjet printing, etc.), or may be formed using a decorative coating agent such as a stone finish coating material or a multicolored pattern paint. It may be.

The pattern film is obtained by applying such a coating agent onto a base material by on-site painting, factory painting (line painting), or the like. Such a coating agent may be, for example, a room temperature drying type, a room temperature curing type, a baking curing type, an ultraviolet (UV) curing type, an electron beam curing type, or the like.

The coating material set of the present invention can be applied to patterned coating surfaces as described above. The patterned coating surface may be newly installed or may be one that has deteriorated over time (existing coating), but the coating material set of the present invention can be used for repainting when the patterned coating surface has deteriorated over time ( It can be preferably applied for (renovation). Although the degree of deterioration over time is not particularly limited, walls that have been used for approximately 5 years or more (even 8 years or more) are suitable as objects of the present invention. Before forming the laminated film, cleaning or partial repair of the existing film surface can be performed as necessary. If the existing coating surface has a joint material such as a sealant, the existing joint material may be left as is, but it is also possible to place a new joint material before forming the laminated coating, or to remove the existing joint material. It is also possible to apply treatments such as painting to the surface of the material.

In particular, the present invention provides that the film located on the outermost surface of the patterned film surface is an inorganic film (a film containing the above-mentioned inorganic binder), an organic-inorganic composite film (a film containing the above-mentioned organic-inorganic composite binder), a fluororesin film (a film containing the above-mentioned organic-inorganic composite binder), It is suitable when the film is one or more selected from the above-mentioned films containing fluororesin, etc., and furthermore, it can be preferably applied when these are transparent films.

The thickness of the laminated film newly formed by the first covering material and the second covering material is preferably 30 μm or more, more preferably 50 μm or more, even more preferably 60 μm or more, particularly preferably more than 65 μm, and most preferably 70 μm. That's all. By keeping the lower limit of the film thickness within the above range, the laminated film has sufficient resistance to sunlight and water, suppresses deterioration such as discoloration and cracking caused by the patterned film surface, and maintains its aesthetic appearance over a long period of time. It is suitable in this respect. The upper limit of the thickness of the laminated film is not particularly limited, but is preferably 300 μm or less, more preferably 250 μm or less, and even more preferably 200 μm or less. If the upper limit of the film thickness is within the above range, a finish that takes advantage of the design of the patterned coating surface can be obtained. Note that the film thickness in the present invention is a dry film thickness.

The film thickness ratio between the film of the first coating material and the film of the second coating material {(thickness of the film of the first coating material):(film thickness of the film of the second coating material)} is preferably 80:20. ~20:80, more preferably 70:30~30:70, even more preferably 65:35~35:65. With this aspect, sufficient effects can be obtained in terms of suppressing discoloration, cracking, etc. caused by the pattern coating surface, improving adhesion to the pattern coating surface, maintaining aesthetic appearance over a long period of time, etc. .

The first coating material and the second coating material can each be coated multiple times. It is also possible to overcoat two or more types of coating material corresponding to the first coating material, or to overcoat two or more types of coating material corresponding to the second coating material. For example, two or more types with different colors and degrees of gloss, such as a colorless transparent type, a colored transparent type, a glossy type, and a matte type, can be coated over each other. When recoating, appropriate intervals may be provided to allow the film to dry. In such a case, it is desirable that the film thickness after recoating satisfies the above conditions. In addition, when two or more types of first coating materials are coated, it is desirable that at least the bottom layer (patterned coating surface side) of the first coating materials satisfies r ₁ and/or s ₁ above. When two or more types of second coating materials are coated, it is desirable that at least the uppermost layer (surface side) of the second coating materials satisfies r ₂ and/or s ₂ above.

In applying each coating material, known painting equipment can be used. As the painting tool, for example, a spray, a roller, a brush, etc. can be used. It is desirable that the amount of each coating material applied, the number of coats, etc. be set so that the final film thickness is within the above range. The coating amounts of the first coating material and the second coating material are preferably 0.05 to 0.4 kg/m ² , more preferably 0.08 to 0.3 kg/m ² . The number of coats of each coating material is preferably 1 to 3 times. At the time of painting, each coating material can be diluted as necessary. Drying after application of each coating material may be carried out at room temperature (preferably 0 to 50°C, more preferably 5 to 45°C), and may be heated if necessary.

Examples are shown below to clarify the features of the present invention.
The following covering materials were prepared.

・Coating material 1: Binding material 1 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane (weight ratio 20: Composite of emulsion polymer (52:23:2:1:1:1) and alkoxysilane compound, component (A) 72% by weight in the resin constituents, r = 0.72, s = 0.5% by weight }, a mixture of a thickener, a coalescing agent, an antifoaming agent, and water. Visible light transmittance 62%, UV transmittance 5%.

・Coating material 2: Binding material 2 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane (weight ratio 25: Composite of emulsion polymer (40:30:2:1:1:1) and alkoxysilane compound, component (A) 65% by weight in the resin constituents, r = 0.62, s = 0.5% by weight }, a mixture of a thickener, a coalescing agent, an antifoaming agent, and water. Visible light transmittance 63%, UV transmittance 4%.

・Coating material 3: Binding material 3 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane (weight ratio 25: Composite of emulsion polymer (30:40:2:1:1:1) and alkoxysilane compound, component (A) 55% by weight in the resin constituents, r = 0.55, s = 0.5% by weight }, a mixture of a thickener, a coalescing agent, an antifoaming agent, and water. Visible light transmittance 63%, UV transmittance 5%.

・Coating material 4: Binding material 4 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane (weight ratio 32: Composite of emulsion polymer (18:45:2:1:1:1) and alkoxysilane compound, component (A) 50% by weight in the resin constituents, r = 0.36, s = 0.5% by weight }, a mixture of a thickener, a coalescing agent, an antifoaming agent, and water. Visible light transmittance 62%, UV transmittance 4%.

・Coating material 5: Binding material 5 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid (weight ratio 25:30:40:2:1:2 ), a mixture of component (A) (55% by weight, r=0.55, s=0% by weight), a thickener, a film-forming aid, an antifoaming agent, and water. Visible light transmittance 65%, UV transmittance 5%.

・Coating material 6: Binding material 6 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid (weight ratio 32:18:45:2:1:2 ), a mixture of component (A) in the resin components: 50% by weight, r=0.36, s=0% by weight}, a thickener, a film-forming aid, an antifoaming agent, and water. Visible light transmittance 64%, UV transmittance 5%.

・Coating material 7: Binding material 7 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane (weight ratio 28: 12:55:2:1:1:1) composite of emulsion polymer and alkoxysilane compound, component (A) 40% by weight in the resin constituents, r = 0.30, s = 0.5% by weight }, a mixture of a thickener, a coalescing agent, an antifoaming agent, and water. Visible light transmittance 62%, UV transmittance 4%.

・Coating material 8: Binding material 8 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane (weight ratio 46: Composite of emulsion polymer (4:45:2:1:1:1) and alkoxysilane compound, component (A) 50% by weight in the resin constituents, r = 0.08, s = 0.5% by weight }, a mixture of a thickener, a coalescing agent, an antifoaming agent, and water. Visible light transmittance 61%, UV transmittance 6%.

・Coating material 9: Binding material 9 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, monomer containing a photostable group, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane (weight ratio 25:30:42:1:1) : Composite of emulsion polymer of 1) and alkoxysilane compound, component (A) in the resin constituents 55% by weight, r=0.55, s=0.5% by weight}, thickener, film forming aid A mixture of an antifoaming agent, an antifoaming agent, water, and a triazine ultraviolet absorber (0.3 parts by weight per 100 parts by weight of the resin component). Visible light transmittance 61%, UV transmittance 24%.

・Coating material 10: Binding material 10 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, monomer containing a photostable group, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane (weight ratio 32:18:47:1:1) : Composite of emulsion polymer of 1) and alkoxysilane compound, (50% by weight of component (A) in the resin constituents, r = 0.36, s = 0.5% by weight}, thickener, film forming aid) A mixture of an antifoaming agent, an antifoaming agent, water, and a triazine ultraviolet absorber (0.3 parts by weight per 100 parts by weight of the resin component). Visible light transmittance 60%, UV transmittance 26%.

・Coating material 11: Binding material 11 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane (weight ratio 25: 30:39:2:1:1:2) composite of emulsion polymer and alkoxysilane compound, component (A) 55% by weight in the resin constituents, r = 0.55, s = 3.0% by weight }, a mixture of a thickener, a coalescing agent, an antifoaming agent, and water. Visible light transmittance 62%, UV transmittance 4%.

・Coating material 12: Binding material 12 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane (weight ratio 25: Composite of emulsion polymer (30:39:2:1:1:2) and alkoxysilane compound, component (A) 55% by weight in the resin constituents, r = 0.55, s = 4.5% by weight }, a mixture of a thickener, a coalescing agent, an antifoaming agent, and water. Visible light transmittance 61%, UV transmittance 4%.

・Coating material 13: Binding material 13 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane, glycidyl methacrylate (weight A composite of an emulsion polymer and an alkoxysilane compound with a ratio of 24:30:39:2:1:1:2:1), component (A) in the resin component 54% by weight, r = 0.56, s = 4.5% by weight}, a mixture of thickener, coalescent, antifoaming agent, and water. Visible light transmittance 61%, UV transmittance 4%.

・Coating material 14: Binding material 14 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane, glycidyl methacrylate (weight A composite of an emulsion polymer and an alkoxysilane compound with a ratio of 24:40:29:2:1:1:2:1), component (A) 64% by weight in the resin components, r = 0.63, s = 4.5% by weight}, a mixture of thickener, coalescent, antifoaming agent, and water. Visible light transmittance 61%, UV transmittance 5%.

・Coating material 15: Binding material 15 {cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ultraviolet absorbing group-containing monomer, photostable group-containing monomer, acrylic acid (weight ratio 10:8:78:2:1:1) ), a mixture of component (A) in the resin components: 18% by weight, r=0.44, s=0% by weight}, a thickener, a film-forming aid, an antifoaming agent, and water. Visible light transmittance 60%, UV transmittance 5%.

・Coating material 16: Binding material 16 {emulsion polymer of cyclohexyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, and acrylic acid (weight ratio 10:8:81:1), component (A) 18% by weight among the resin components, r=0.44, s=0% by weight}, a mixture of a thickener, a coalescing agent, an antifoaming agent, and water. Visible light transmittance 59%, UV transmittance 55%.

(Example 1)
The existing coating surface is a ceramic siding boat that has deteriorated due to outdoor exposure (the surface has a tile-like uneven pattern, a black acrylic resin coating is applied to the concave areas, a brown acrylic resin coating is applied to the convex areas, and the entire surface is acrylic). (having a transparent silicone resin coating) was prepared. Coating material 1 was spray-painted as the first coating material over the entire surface of this existing coating surface so that the dry film thickness (denoted as "film thickness" in Table 1. The same applies hereinafter) was 38 μm, and after drying for 3 hours. A test specimen was prepared by spray-coating coating material 2 as a second coating material so that the dry film thickness was 38 μm, and drying and curing for 7 days. The painting and curing steps were all performed under standard conditions (temperature 23° C., relative humidity 50%).

[Test I]
The adhesion of the test specimens obtained by the above method was evaluated using a checkerboard tape method according to JIS K5600-5-6. The evaluation criteria are "A: Defect area is less than 10%,""B: Defect area is 10% or more and less than 30%,""C: Defect area is 30% or more and less than 50%," and "D: Defect area is 30% or more and less than 50%." 50% or more of the area. The test results are shown in Table 1.

[Test II]
For the test specimens obtained by the above method, an iSuper UV tester (manufactured by Iwasaki Electric Co., Ltd.) was used as an accelerated weathering tester, and one cycle consisted of 6 hours of light irradiation and 2 hours of dew condensation (8 hours in total), up to 60 cycles. An accelerated test was conducted. At this time, changes in appearance (crack state) on the surface of the specimen were observed at the end of the 20th cycle, at the end of the 40th cycle, and at the end of the 60th cycle, and the color difference before and after acceleration was measured. Appearance changes were evaluated on a four-level scale (Excellent; A>B>C>D; Poor): "A: No change" and "D: Cracking progressed." The color difference was evaluated as "A: Color difference less than 1,""B: Color difference 1 or more and less than 3,""C: Color difference 3 or more and less than 10," and "D: Color difference 10 or more." The test results are shown in Table 1.

(Example 2)
A test body was prepared in the same manner as in Example 1, except that Coating Material 1 was used as the first coating material and Coating Material 3 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.

(Example 3)
A test body was prepared in the same manner as in Example 1, except that coating material 2 was used as the first coating material and coating material 4 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.

(Example 4)
A test body was prepared in the same manner as in Example 1, except that coating material 3 was used as the first coating material and coating material 4 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.

(Example 5)
A test body was prepared in the same manner as in Example 1, except that coating material 3 was used as the first coating material and coating material 7 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.

(Example 6)
A test body was prepared in the same manner as in Example 1, except that coating material 5 was used as the first coating material and coating material 6 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.

(Example 7)
A test body was prepared in the same manner as in Example 1, except that coating material 4 was used as the first coating material and coating material 8 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.

(Example 8)
A test body was prepared in the same manner as in Example 1, except that coating material 9 was used as the first coating material and coating material 10 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.

(Example 9)
A test body was prepared in the same manner as in Example 2, except that the first coating material and the second coating material were coated so that each had a dry film thickness of 12 μm, and the same tests were conducted. The test results are shown in Table 1.

(Example 10)
Except for using coating material 11 as the first coating material and coating material 4 as the second coating material, a test specimen was prepared in the same manner as in Example 1, and a test was carried out in the same manner. The test results are shown in Table 1.

(Example 11)
A test body was prepared in the same manner as in Example 1, except that coating material 12 was used as the first coating material and coating material 4 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.

(Example 12)
A test body was prepared in the same manner as in Example 1, except that coating material 13 was used as the first coating material and coating material 4 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.

(Example 13)
A test body was prepared in the same manner as in Example 1, except that coating material 14 was used as the first coating material and coating material 4 was used as the second coating material, and the same tests were conducted. The test results are shown in Table 1.

(Comparative example 1)
A test body was prepared in the same manner as in Example 1, except that coating material 15 was used as the first coating material and the second coating material, and the same test was conducted. The test results are shown in Table 1.

(Comparative example 2)
A test body was prepared in the same manner as in Example 1, except that coating material 16 was used as the first coating material and the second coating material, and the same test was conducted. The test results are shown in Table 1.

[Test III]
The test specimens of Examples 1 to 13 were exposed outdoors for 6 months, and changes in appearance due to dirt, etc. on the surface of the test specimens were observed. Those with a slight degree of dirt were rated "A" (4 grades: excellent; A>B>C>D; poor). The test results are shown in Table 1.

(Example 14)
The existing coating surface is a ceramic siding boat that has deteriorated due to outdoor exposure.The surface has protrusions and depressions (joints) similar to tile joints, and the protrusions have an irregular pattern of irregularities, and an inorganic clear coating is used as the top layer coating. one with a coating} was prepared. Coating material 2 was spray-coated as the first coating material to a dry film thickness of 38 μm over the entire surface of the existing coating surface, and after drying for 3 hours, coating material 4 was applied as the second coating material to a dry film thickness of 38 μm. A test specimen was prepared by spray painting and drying and curing for 7 days. All painting and curing processes were performed under standard conditions. This test specimen uses the same covering material as in Example 3 above.

[Test IV]
The adhesion of the test specimens obtained by the above method was evaluated using a checkerboard tape method according to JIS K5600-5-6. The evaluation criteria are the same as in [Test I] above. The test results are shown in Table 2.

[Test V]
For the test specimens obtained by the above method, an iSuper UV tester (manufactured by Iwasaki Electric Co., Ltd.) was used as an accelerated weathering tester, and one cycle consisted of 6 hours of light irradiation and 2 hours of dew condensation (8 hours in total), up to 60 cycles. An accelerated test was conducted. At this time, changes in appearance (crack state) on the surface of the specimen were observed at the end of the 20th cycle, at the end of the 40th cycle, and at the end of the 60th cycle, and the color difference before and after acceleration was measured. The evaluation criteria are the same as in [Test II] above. The test results are shown in Table 2.

(Example 15)
A test body was prepared in the same manner as in Example 14, except that coating material 3 was used as the first coating material and coating material 4 was used as the second coating material, and the same test was conducted. This test specimen uses the same covering material as in Example 4 above. The test results are shown in Table 2.

(Example 16)
A test body was prepared in the same manner as in Example 14, except that coating material 3 was used as the first coating material and coating material 7 was used as the second coating material, and the same tests were conducted. This test specimen uses the same covering material as in Example 5 above. The test results are shown in Table 2.

(Example 17)
A test body was prepared in the same manner as in Example 14, except that coating material 5 was used as the first coating material and coating material 6 was used as the second coating material, and the same test was conducted. This test specimen uses the same covering material as in Example 6 above. The test results are shown in Table 2.

(Example 18)
A test body was prepared in the same manner as in Example 14, except that coating material 11 was used as the first coating material and coating material 4 was used as the second coating material, and the same tests were conducted. This test specimen uses the same covering material as in Example 10 above. The test results are shown in Table 2.

(Example 19)
A test body was prepared in the same manner as in Example 14, except that coating material 12 was used as the first coating material and coating material 4 was used as the second coating material, and the same test was conducted. This test specimen uses the same covering material as in Example 11 above. The test results are shown in Table 2.

(Example 20)
A test body was prepared in the same manner as in Example 14, except that coating material 13 was used as the first coating material and coating material 4 was used as the second coating material, and the same test was conducted. This test specimen uses the same covering material as in Example 12 above. The test results are shown in Table 2.

(Example 21)
A test body was prepared in the same manner as in Example 14, except that coating material 14 was used as the first coating material and coating material 4 was used as the second coating material, and the same test was conducted. This test specimen uses the same covering material as in Example 13 above. The test results are shown in Table 2.

Claims (5)

A coating material set for forming a transparent laminated film,
The covering material set includes at least a first covering material and a second covering material,
The first covering material and the second covering material are each
(meth)acrylic acid alkyl ester (A) having an alkyl group having 3 or more carbon atoms selected from cyclohexyl methacrylate and 2-ethylhexyl acrylate , and methyl methacrylate as resin constituents,
selected from reactive silyl group-containing monomers, reactive silyl group-containing mercapto compounds, silane coupling agents, tetrafunctional alkoxysilane compounds, trifunctional alkoxysilane compounds, bifunctional alkoxysilane compounds, siloxane compounds, or polycondensates thereof A binder containing an inorganic component derived from one or more silicon compounds ,
The above component (A) contains 2-ethylhexyl acrylate (a1),
The ratio of cyclohexyl methacrylate in the resin constituent components is 20 to 46% by weight, the ratio of 2-ethylhexyl acrylate is 4 to 52% by weight, and the ratio of methyl methacrylate is 23 to 55% by weight,
If the weight ratio of the component (a1) in the component (A) is r,
r (r ₁ ) in the binding material of the first covering material is larger than r (r ₂ ) in the binding material of the second covering material ,
The first coating material and the second coating material each form a coating having a visible light transmittance of 30% or more.
A covering material set characterized by: 2. The dressing set according to claim 1, wherein the first covering material and the second covering material each form a film having an ultraviolet transmittance of 30% or less. If the weight ratio of the inorganic content to the nonvolatile content of the binder is s, then
The dressing set according to claim 1 or 2, wherein s (s ₁ ) in the binding material of the first dressing material is larger than s (s ₂ ) in the binding material of the second dressing material.
(However, the weight ratio s of the inorganic content to the nonvolatile content of the binder is a value calculated using the following formula.
[Formula] s (weight %) = {Weight of inorganic components contained in the binder} / {Weight of non-volatile components of the binder} x 100
(The "weight of non-volatile content of the binder" and the "weight of inorganic content contained in the binder" are measured according to the method of JIS K 5601-1-2 "Heating residue". "Weight of inorganic components contained in the binder" is the value measured at a heating temperature of 135°C and a heating time of 60 minutes. This is the value when measured under the following conditions.)) If the weight ratio of the inorganic content to the nonvolatile content of the binder is s, then
s(s ₁ ) is 0.1 to 20% by weight, and s (s ₂ ) is 0.01 to 10% by weight, the dressing set according to any one of claims 1 to 3. The coating material set according to any one of claims 1 to 4, wherein the first coating material is a base coating material and the second coating material is a top coating material.