JP7128125B2 - Coating method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a film forming method applicable to buildings and the like.

BACKGROUND ART Conventionally, various types of coating materials have been used to form coatings on various substrates, such as exterior wall surfaces of buildings, for the purpose of protecting the substrates and improving the aesthetic appearance of the substrates. Such wall surfaces are often provided with an uneven pattern or a colored pattern from the viewpoint of aesthetics. However, since such wall surfaces (existing wall surfaces) are exposed to the outdoors for a long period of time, deterioration progresses under the influence of sunlight, rainfall, etc., and the initial aesthetic appearance deteriorates over time.

On the other hand, in recent years, there is a movement to repaint the existing wall surface to improve aesthetics and extend the life of the base material. For example, Patent Document 1 describes a method of applying a transparent coating agent as a topcoat material after polishing the deteriorated portion of the surface of the coating layer of the ceramic exterior wall material.

Japanese Unexamined Patent Application Publication No. 2001-227138

However, even if the existing wall surface having an uneven pattern is repainted by the method described in the above patent document, deterioration of the existing coating cannot be sufficiently suppressed, and the effect of repainting cannot be obtained. There is

The present invention has been devised in view of such problems, and provides a method of forming a film that can suppress the deterioration of the existing film and maintain the aesthetic appearance for a long time while making use of the uneven pattern and color pattern of the existing wall surface. intended to

In order to solve such problems, the present inventors have made intensive studies, and as a result, have come up with a coating formation method for forming a coating by applying a specific topcoat material to an existing wall surface having an uneven pattern. I came to complete it.

That is, the present invention has the following features.
1. A film forming method for applying a topcoat material to an existing wall surface that has deteriorated over time,
The existing wall surface has an uneven pattern on the surface and is provided with an existing coating,
The topcoat material contains a non-aqueous solvent (A), a resin component (B), and a thickener (C),
The non-aqueous solvent (A) contains a non-aqueous solvent having an aniline point of 12 to 70 ° C.,
The resin component (B) is composed of one or more compounds, at least one of which is a compound having a reactive silyl group,
The solid content of the resin component (B) is 25 to 75% by weight in the topcoat material,
A method of forming a film, wherein the topcoat material is transparent to visible light and forms a film having an ultraviolet transmittance of 30% or less.
2. The resin component (B) consists of one or more compounds,
1. At least one of the compounds is a resin having a weight average molecular weight of 10,000 to 150,000. The described coating method.
3. The existing wall surface has an uneven pattern on the surface and is composed of a plurality of plate-like wall materials provided with an existing coating. or 2. The film forming method according to .

In the present invention, it is possible to obtain a finish that takes advantage of the uneven pattern and color pattern of the existing wall surface by a new coating formed from a specific topcoat material. In addition, in the present invention, the new coating sufficiently suppresses the deterioration of the existing coating, so that the aesthetic appearance can be maintained for a long period of time.

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

INDUSTRIAL APPLICABILITY The present invention can be applied to existing wall surfaces of buildings, civil engineering structures, and the like. Such an existing wall surface is composed of at least a base material and an existing coating. Examples of the base material include concrete, mortar, metal, wood, glass, and various plate-shaped wall materials. Of these, the plate-shaped wall material includes, for example, an inorganic hardened material containing cement, calcium silicate, lime, gypsum, or the like as a main component. Specific examples of such plate-like wall materials include cement boards, extruded boards, slate boards, PC boards, ALC boards, fiber-reinforced cement boards, siding boards, ceramic boards, calcium silicate boards, gypsum boards, and hard boards. Examples include wood chips, cement boards, and the like.

In the present invention, an existing wall surface having an uneven pattern on its surface is targeted. Various uneven patterns on the existing wall surface include tile patterns, brick patterns, geometric patterns, striped patterns, lattice patterns, polka dot patterns, sand wall patterns, citrus skin patterns, ripple patterns, and others. , patterns designed with animals and plants, and the like. Concretely, the shape of the convex portion when the concave-convex pattern is viewed from the front includes, for example, a square, rectangle, circle, ellipse, triangle, rhombus, polygon, irregular shape, and the like. Moreover, the cross-sectional shape of the projections in the uneven pattern includes, for example, trapezoid, square, rectangle, semicircle, wave, staircase, triangle, chevron, and the like. Concave portions in the concave-convex pattern include, for example, those that are flat and form joints. The height difference between the concave portion and the convex portion may be constant or different at each site, but is preferably 20 mm or less, more preferably about 1 to 15 mm. Such an uneven pattern may be applied to one or both of the base material and the existing coating.

In the existing wall surface of the present invention, the existing coating is provided on the surface of the substrate, and the existing wall surface can have various colors (single color or multicolor pattern). Existing coatings are various coatings that have already been coated on the base material by on-site coating, factory coating (line coating), etc., for example, at least selected from organic coatings, inorganic coatings, organic-inorganic composite coatings, etc. One type of coating is mentioned. In addition, existing coatings include colored coatings (enamel-based coatings, printed coatings, etc.), clear coatings, or laminated coatings of these, etc., which are coatings formed by applying and curing various coating materials to the substrate. . Such a coating material may be, for example, any of room temperature drying type, room temperature curing type, baking curing type, ultraviolet (UV) curing type, electron beam curing type, and the like.

Examples of binders for such coating materials include organic binders such as acrylic resins, polyurethane resins, epoxy resins, fluorine resins, alkyd resins, and polyester resins, silicone resins, alkoxysilanes, colloidal silica, silicates, and the like. and organic/inorganic composite binders such as acrylic silicone resins.

In the present invention, in particular, the existing coating on the outermost surface is an inorganic coating (coating containing the inorganic binder), an organic-inorganic composite coating (coating containing the organic-inorganic composite binding), or a fluororesin coating (containing the fluororesin). coating), etc., and can be preferably applied to these clear coatings. Such an existing coating may contain photocatalytic titanium oxide or the like.

INDUSTRIAL APPLICABILITY The present invention can be applied as a renovation method when the existing wall surface as described above has deteriorated over time. The degree of deterioration over time is not particularly limited, but wall surfaces that have been used for approximately 5 years or more (or 8 years or more) can be covered by the present invention.

As the existing wall surface of the present invention, it is preferable that a plurality of plate-like wall materials having an uneven pattern on the surface and having an existing film are arranged side by side. Advantageous effects can be obtained when the present invention is directed to an existing wall surface composed of such a plurality of plate-like wall materials. It is desirable that the uneven pattern is applied at least to the plate-shaped wall material itself.
A sealing material or a dry joint material may be filled in the joints between the plate-like wall materials. In this case, the plurality of plate-like wall materials are juxtaposed through connecting portions, and the connecting portions are provided between the plate-like wall materials. The width of the connecting portion is preferably about 3 to 20 mm (more preferably 5 to 15 mm). This connecting portion is filled with a sealing material or a dry joint compound.

In the present invention, an advantageous effect can be obtained when the existing wall surface is formed by filling the connecting portions of the plate-like wall materials with the sealing material. The sealing material may be one that has deteriorated over time in the same manner as the plate-like wall material, or it may be one that has been newly placed before the coating of the topcoat material.

Common sealants can be used, for example, silicone-based sealants, modified silicone-based sealants, polysulfide-based sealants, modified polysulfide-based sealants, acrylic urethane-based sealants, polyurethane-based sealants, and SBR. and butyl rubber-based sealing materials.
A method of filling the sealing material is not particularly limited, and for example, a known method using a gun, a spatula, or the like can be adopted.

Before filling with the sealing material, a treatment such as filling with a backup material or applying a primer may be performed in advance. As the backup material, for example, a foamed polyethylene-based backup material or the like can be used. Examples of primers that can be used include synthetic rubber primers, acrylic primers, urethane primers, epoxy primers, silicone resin primers, and silane primers.

The film formation method of the present invention is to apply (paint) a topcoat material to the existing wall surface that has deteriorated over time as described above.

The topcoat material in the present invention contains a non-aqueous solvent (A), a resin component (B), and a thickener (C), of which the non-aqueous solvent (A) and the resin component (B) each contain a specific compound. Including, the solid content of the resin component (B) in the topcoat material, the ultraviolet transmittance, etc. are characterized by being within a specific range.

In the present invention, by using such a topcoat material, it is possible to obtain a finish that makes use of the uneven pattern and color pattern on an existing wall surface having an uneven pattern and an existing coating. It is possible to sufficiently suppress the deterioration of the coating and form a new coating that contributes to the long-term maintenance of aesthetic appearance. In the present invention, such new coating can extend the life of the existing wall surface. Although the action mechanism of such an effect is not limited to the following, the topcoat material in the present invention contains a thickener, and the solid content of the resin component satisfies specific conditions, etc., so that the existing existing coating material can be used. It can be applied evenly along the unevenness of the wall surface, and the topcoat material applied to the existing wall surface exhibits excellent adhesion to the existing coating due to the action of specific non-aqueous solvents and resin components. presumed to be contributing. In the present invention, such a new coating increases resistance to sunlight and water, and effects such as suppression of deterioration of the existing coating and long-term maintenance of aesthetic appearance can be obtained.

In addition, on an existing wall surface having an uneven pattern and an existing coating, the way sunlight hits the wall, the way water flows, the degree of retention, etc. partially differ depending on the shape of the unevenness and the like. Therefore, in the prior art, even after the coating of the topcoat material, deterioration progresses in areas where the load due to sunlight and water is large, and there is a possibility that local discoloration, cracks, etc. may be caused. On the other hand, in the present invention, the new coating formed from the above-mentioned specific topcoat material is formed over the entire surface of the existing wall surface having an uneven pattern, and exhibits sufficient resistance to sunlight and water. It is thought that deterioration of the film can be suppressed, and effects such as long-term maintenance of aesthetic appearance can be obtained.

Non-aqueous solvent (A) in the topcoat material, for example, n-heptane, n-hexane, n-pentane, n-octane, n-nonane, n-decane, n-undecane, n- aliphatic such as dodecane Hydrocarbon solvents, alicyclic hydrocarbon solvents such as methylcyclohexane and ethylcyclohexane, mixed solvents containing aliphatic hydrocarbons such as mineral spirits, petroleum solvents such as petroleum ether, petroleum naphtha, solvent naphtha, kerosene, and isoparaffin system solvents, alcohol solvents, ether alcohol solvents, ether solvents, ester solvents, ether ester solvents, ketone solvents and the like. These can be used singly or in combination of two or more.

The topcoat material in the present invention contains a non-aqueous solvent having an aniline point of 12 to 70° C. as the non-aqueous solvent (A). Such a non-aqueous solvent is considered to contribute to the improvement of adhesion by slightly swelling or dissolving the existing film. Examples of the non-aqueous solvent having an aniline point of 12 to 70°C include one or more selected from aliphatic hydrocarbon-containing mixed solvents such as mineral spirits, petroleum solvents such as petroleum ether, petroleum naphtha, solvent naphtha, and kerosene. preferred. In the present invention, it is more preferable that the non-aqueous solvent (A) contains a non-aqueous solvent having an aniline point of 30 to 65°C. An aspect containing 50 to 100% by weight is more preferable. The aniline point is a value measured by the method of JIS K2256. 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 resin component (B) in the topcoat material consists of one or more compounds, at least one of which is a compound having a reactive silyl group. A compound having such a reactive silyl group is considered to contribute to the improvement of adhesion due to its cross-linking reactivity.

The reactive silyl group is one in which one or more functional groups selected from, for example, an alkoxyl group, hydroxyl group, phenoxy group, mercapto group, amino group, halogen, etc. are bonded to a silicon atom. Among these, an alkoxysilyl group in which an alkoxyl group is bonded to a silicon atom and/or a silanol group in which a hydroxyl group is bonded to a silicon atom are preferable.

Examples of compounds having a reactive silyl group include reactive silyl group-containing vinyl compounds, tetraalkoxysilane compounds, alkylalkoxysilane compounds, silane coupling agents, etc., or compounds derived from these (e.g., condensates, modified products, polymers, copolymers, etc.). These can be used singly or in combination of two or more.

Among them, examples of reactive silyl group-containing vinyl compounds include γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, , γ-(meth)acryloxypropylmethyldiethoxysilane and the like.

The reactive silyl group-containing vinyl compound can be used in the form of a resin obtained by copolymerization with other monomers (for example, acrylic silicone resin, etc.). Examples of such monomers include (meth)acrylic acid alkyl esters, hydroxyl group-containing monomers, carboxyl group-containing monomers, amino group-containing monomers, pyridine-based monomers, nitrile group-containing monomers, amide group-containing monomers, epoxy group-containing monomers, Carbonyl group-containing monomers, fluorine-containing monomers, aromatic monomers, UV-absorbing group-containing monomers, photostable group-containing monomers, and the like can be mentioned. These can be used singly or in combination of two or more. In the present invention, both acrylic acid alkyl ester and methacrylic acid alkyl ester are collectively referred to as (meth)acrylic acid alkyl ester. A monomer is a general term for compounds having a polymerizable unsaturated double bond.

Tetraalkoxysilane compounds include, for example, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, and the like.

Examples of alkylalkoxysilane compounds include methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyl trimethoxysilane, butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dipropyldimethoxysilane silane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane and the like.

Examples of silane coupling agents include epoxy group-containing silanes such as γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyltriethoxysilane, β-(3,4 epoxycyclohexyl)ethyltrimethoxysilane. Coupling agents, amino group-containing silane coupling agents such as N-β (aminoethyl) γ-aminopropylmethyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and isocyanate group-containing Examples include silane coupling agents, isocyanurate group-containing silane coupling agents, acid anhydride group (carboxyl group)-containing silane coupling agents, and the like.

The resin component (B) can contain compounds other than the compound having a reactive silyl group. Examples of such compounds include various resins such as acrylic resins, polyester resins, polyether resins, polyurethane resins, fluorine resins, vinyl acetate resins, and epoxy resins, or various compounds capable of producing these resins. can be mentioned.

At least one resin component (B) is desirably a resin having a weight average molecular weight of 10,000 to 150,000 (more preferably 40,000 to 120,000, still more preferably 55,000 to 95,000). In the present invention, when a resin with such a weight-average molecular weight is contained, the topcoat material can be easily applied evenly along the unevenness of the existing wall surface, suppressing deterioration of the existing coating, maintaining aesthetic appearance over a long period of time. be. In addition, a weight average molecular weight is a value obtained by measuring using a gel permeation chromatography.

At least one resin component (B) is desirably a non-aqueous dispersion type resin. The non-aqueous-dispersible resin is dispersed as resin particles in the non-aqueous solvent (A), and has both a resin portion that is soluble in the non-aqueous solvent (A) and a resin portion that is not soluble in the non-aqueous solvent (A). . When the resin component (B) contains a resin in such a form, the topcoat material can be easily applied evenly along the unevenness of the existing wall surface. is.

Such a resin preferably has a glass transition point of -40 to 60°C, more preferably -20 to 55°C. When the glass transition point is equal to or higher than the above lower limit, it is preferable in terms of contamination suppression and maintenance of aesthetic appearance. preferred. The glass transition temperature is a value determined by the Fox formula.

One preferred embodiment of the resin component (B) is, for example, an embodiment containing a resin obtained by copolymerization of a reactive silyl group-containing vinyl compound and a monomer other than this. In this embodiment, for example, a (meth)acrylic acid alkyl ester or the like can be used as a monomer to be copolymerized with the reactive silyl group-containing vinyl compound. Such a resin desirably satisfies the above conditions such as weight average molecular weight and morphology.

In this aspect, one or more selected from tetraalkoxysilane compounds, alkylalkoxysilane compounds, silane coupling agents, condensates and/or modified products thereof can be used in combination. Moreover, a curing catalyst can also be used together. Examples of curing catalysts include organic tin compounds, organic aluminum compounds, organic titanate compounds, acidic compounds, amine compounds, alkaline compounds, and the like, and these can be used singly or in combination of two or more.

As one preferred embodiment of the resin component (B), the resin component (B) is composed of two or more compounds, at least one of which is a hydroxyl group-containing resin and at least one of which is a polyisocyanate compound. A certain aspect can also be mentioned. Both of these components can be reactively cured during film formation to form a polyurethane resin film.

Specific examples of such aspects include the following (1) and (2).
(1) An embodiment in which the resin component (B) is composed of two or more compounds, at least one of which is a hydroxyl group-containing resin having a reactive silyl group, and at least one of which is a polyisocyanate compound.
(2) the resin component (B) is composed of three or more compounds, at least one of which is a hydroxyl group-containing resin and at least one is a polyisocyanate compound;
An embodiment in which at least one is a compound having a reactive silyl group.

In the aspect (1) above, as the hydroxyl group-containing resin having a reactive silyl group, for example, a resin containing a reactive silyl group-containing vinyl compound, a (meth)acrylic acid alkyl ester, and a hydroxyl group-containing monomer as resin constituents is used. can.

The (meth)acrylic acid alkyl ester is a compound having a (meth)acryloyl group and an alkyl group, and examples of the form of the alkyl group include linear, branched, and cyclic.

Examples of such (meth)acrylic acid alkyl esters include those having an alkyl group having 1 to 2 carbon atoms such as methyl (meth)acrylate and ethyl (meth)acrylate, or (meth)acrylic acid n -propyl, 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, (meth)acrylic acid n-hexyl, cyclohexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, 2-methylpentyl (meth)acrylate, 4-methylpentyl (meth)acrylate, n-heptyl (meth)acrylate, ( n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-undecyl (meth)acrylate and those having an alkyl group having 3 or more carbon atoms such as n-lauryl (meth)acrylate. These can be used singly or in combination of two or more.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ( (Meth)acrylic acid hydroxyalkyl esters such as 4-hydroxybutyl methacrylate and the like. These can be used singly or in combination of two or more.

Such a hydroxyl-containing resin desirably satisfies the conditions such as the weight-average molecular weight and morphology described above. Its hydroxyl value is preferably 10 to 200 KOHmg/g, more preferably 20 to 100 KOHmg/g. 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 resin solid content.

The polyisocyanate compound has two or more isocyanate groups in one molecule, and forms a film by cross-linking reaction with the hydroxyl group-containing resin.

Examples of polyisocyanate compounds include toluene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (pure-MDI), polymeric MDI, xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), water Added XDI, hydrogenated MDI, etc., or derivatives thereof (for example, compounds obtained by urethanization reaction, allophanatization reaction, isocyanurate reaction, etc.), those having an allophanate group, allophanate group and isocyanurate group The thing having etc. can also be used. These can be used singly or in combination of two or more.

In the above aspect (1), a compound having a reactive silyl group (excluding a hydroxyl group-containing resin having a reactive silyl group) can be used together. One or more selected from compounds, alkylalkoxysilane compounds, silane coupling agents, etc., or compounds derived from these (e.g., condensates, modified products, polymers, copolymers, etc.) can be used. . In addition, in the aspect (1) above, a curing catalyst can also be used together.

In the above aspect (2), hydroxyl-containing resins (excluding those having reactive silyl groups) can be used. Examples of such hydroxyl group-containing resins include polyether polyols, polyester polyols, acrylic polyols, polyisoprene polyols, carbonate polyols, and the like, and one or more of these can be used. Such a hydroxyl-containing resin desirably satisfies the conditions such as the weight-average molecular weight and morphology described above. The hydroxyl value of the hydroxyl-containing resin is preferably 10 to 200 KOHmg/g, more preferably 20 to 100 KOHmg/g.

In the above aspect (2), the hydroxyl group-containing resin (polyol compound) includes, for example, polyether polyol, polyester polyol, acrylic polyol, fluorine-containing polyol, polyisoprene polyol, carbonate polyol, etc. One or two of these More than one species can be used. The hydroxyl value of the polyol compound is preferably 10-200 KOHmg/g, more preferably 20-100 KOHmg/g.

In the above aspect (2), it is desirable that the hydroxyl group-containing resin (polyol compound) contains one or more selected from acrylic polyols and fluorine-containing polyols.

As the acrylic polyol, a polymer obtained by polymerizing a (meth)acrylic acid alkyl ester, a hydroxyl group-containing monomer, and optionally other monomers as constituent components can be used.

As such (meth)acrylic acid alkyl esters and hydroxyl group-containing monomers, those similar to those described above can be used.

Examples of the other monomers include carboxyl group-containing monomers, amino group-containing monomers, pyridine-based monomers, nitrile group-containing monomers, amide group-containing monomers, epoxy group-containing monomers, carbonyl group-containing monomers, alkoxysilyl group-containing monomers, aromatic group monomers, UV-absorbing group-containing monomers, photostable group-containing monomers, and the like. These can be used singly or in combination of two or more. Incidentally, acrylic polyols having fluorine atoms are included in fluorine-containing polyols.

The acrylic polyol contains 20% by weight or more of a (meth)acrylic acid alkyl ester (M) having an alkyl group having 3 or more carbon atoms (hereinafter also referred to as "(M) component") in the constituent components of the acrylic polyol. is preferred. As such a (M) component, those having an alkyl group with 4 or more carbon atoms (more preferably 4 or more and 8 or less) are more suitable.

The ratio of the (M) component in the acrylic polyol is preferably 20% by weight or more, more preferably 25 to 99% by weight, still more preferably 30 to 98% by weight. When the component (M) is in the above ratio, resistance to water can be enhanced, and deterioration such as discoloration and cracking can be inhibited, and it is also suitable for improving effects such as maintenance of aesthetic appearance.

The acrylic polyol may contain a (meth)acrylic acid alkyl ester (m1) having an alkyl main chain with 4 or more carbon atoms (hereinafter also referred to as "(m1) component") as the (M) component in the resin constituents. preferable. As such component (m1), the alkyl moiety is a linear or branched alkyl group (excluding cyclic), and the main chain (longest straight carbon chain) has 4 or more carbon atoms. one can be used. If the acrylic polyol contains the component (m1), the effects of resistance to water, suppression of deterioration such as cracking, maintenance of aesthetic appearance, and the like can be further enhanced.

Component (m1) has an alkyl main chain with 4 or more carbon atoms (preferably 4 or more and 8 or less) in the alkyl moiety. The alkyl portion of the component (m1) may have various side chains (eg, alkyl groups with fewer carbon atoms than the alkyl main chain) as long as it has such an alkyl main chain. Examples of the (m1) component include those among the above-described (M) components that satisfy these conditions, such as n-butyl (meth)acrylate, 2-methylbutyl (meth)acrylate, and (meth)acrylate. isopentyl acrylate, 3-methylbutyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-pentyl (meth)acrylate, 2-methylpentyl (meth)acrylate, 4-methylpentyl (meth)acrylate , n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-heptyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-(meth)acrylate -nonyl, n-decyl (meth)acrylate, n-undecyl (meth)acrylate, n-lauryl (meth)acrylate and the like. These can be used singly or in combination of two or more.

(M) components other than (m1) (hereinafter also referred to as “(m2) components”) include, for example, n-propyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, (meth) ) t-butyl acrylate, neopentyl (meth)acrylate, t-pentyl (meth)acrylate, 1-ethylpropyl (meth)acrylate, cyclohexyl (meth)acrylate and the like. These can be used singly or in combination of two or more.

The weight ratio of component (m1) in component (M) can be expressed as "r". This "r" is a value calculated by the following formula.
[Formula] r = {weight of component (m1) in resin component}/{weight of component (M) in resin component}

r in the above formula is preferably 0.05 to 0.7, more preferably 0.1 to 0.5, still more preferably 0.15 to 0.4.

When acrylic polyol is included as the polyol compound, the acrylic polyol is preferably contained in the polyol compound in an amount of 30% by weight or more, more preferably 50% by weight or more, and 60% by weight in terms of solid content. is more desirable, and a content of 65% by weight or more is particularly desirable. In the present invention, acrylic polyol alone can also be used as the polyol compound.

A fluorine-containing polyol is a polyol compound having fluorine atoms and hydroxyl groups. The use of a fluorine-containing polyol can enhance the resistance to sunlight and water, and is suitable for improving effects such as suppressing deterioration such as discoloration and cracking and maintaining aesthetic appearance. Such fluorine-containing polyols can be obtained, for example, by copolymerizing fluorine-containing monomers such as fluoroolefins and fluoroalkyl group-containing acrylic monomers, hydroxyl group-containing monomers, and optionally other monomers. can.

Among them, examples of fluoroolefins include vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, 1,1,3,3,3-pentafluoropropylene, 2,2,3,3-tetra Fluoropropylene, 1,1,2-trifluoropropylene, 3,3,3-trifluoropropylene, chlorotrifluoroethylene, bromotrifluoroethylene, 1-chloro-1,2-difluoroethylene, 1,1-dichloro- 2,2-difluoroethylene and the like. Examples of fluoroalkyl group-containing acrylic monomers include perfluoromethyl (meth)acrylate, perfluoroisononylmethyl (meth)acrylate, 2-perfluorooctylethyl (meth)acrylate and the like. These can be used singly or in combination of two or more.

Examples of hydroxyl group-containing monomers include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether and hydroxypentyl vinyl ether; hydroxyallyls such as ethylene glycol monoallyl ether, diethylene glycol monoallyl ether and triethylene glycol monoallyl ether; Ether; (meth)acrylic acid hydroxyalkyl esters similar to those mentioned above, and the like. These can be used singly or in combination of two or more.

When a fluorine-containing polyol is included as the polyol compound, it may be an embodiment in which only the fluorine-containing polyol is included, or an embodiment in which an acrylic polyol and a fluorine-containing polyol are included. Of these, in the embodiment containing acrylic polyol and fluorine-containing polyol, the resistance to sunlight and water can be further enhanced, and sufficient adhesion and the like can be ensured over a long period of time, improving the effects of the present invention. It is preferable in terms of In this case, the acrylic polyol is preferably contained in the polyol compound in an amount of 30 to 99% by weight, more preferably 50 to 95% by weight, and more preferably 60 to 90% by weight in terms of solid content. Desirably, 65 to 85% by weight is particularly desirable. The fluorine-containing polyol is preferably contained in the polyol compound in an amount of 1 to 70% by weight, more preferably 5 to 50% by weight, and even more preferably 10 to 40% by weight, in terms of solid content. A content of 15 to 35% by weight is particularly desirable.

In such an embodiment, it is desirable that at least the acrylic polyol has a weight average molecular weight of 10,000 to 150,000 (more preferably 40,000 to 120,000, still more preferably 55,000 to 95,000). Moreover, it is desirable that at least the acrylic polyol is a non-aqueous dispersion type resin. When these conditions are satisfied, the topcoat material can be easily applied evenly along the unevenness of the existing wall surface, which is preferable in terms of suppressing deterioration of the existing coating and maintaining aesthetic appearance over a long period of time.

As the polyisocyanate compound, those similar to those described above can be used.

In the aspect (2) above, a compound having a reactive silyl group is used. Such compounds include, for example, reactive silyl group-containing vinyl compounds, tetraalkoxysilane compounds, alkylalkoxysilane compounds, silane coupling agents, etc., or compounds derived from these (e.g., condensates, modified products, polymerized , copolymers, etc.) can be used. In particular, in the aspect (2) above, it is desirable to use a tetraalkoxysilane compound and/or its condensate, or its modified product. In the aspect (2) above, a curing catalyst can also be used together.

In the above aspects (1) and (2), the polyisocyanate compound preferably has a number average functional group number of 2 to 3, more preferably 2.05 to 2.6, and 2.1 to 2.1. 2.5 is even more desirable. By using such a polyisocyanate compound, the resistance to water can be enhanced, and the effects of suppressing deterioration such as discoloration and cracking and maintaining aesthetic appearance can be further enhanced. Furthermore, the use of such a polyisocyanate compound is particularly advantageous when the existing wall surface has a sealant, suppressing blistering, cracking, peeling, etc. of the coating in the vicinity of the joint filled with the sealant. and can contribute to the effect of maintaining the finish for a long period of time.

The number average functional group number of the polyisocyanate compound is a value obtained by the following formula. In the formula below, the number average molecular weight of polyisocyanate is a value measured by gel permeation chromatography (GPC). The NCO content is the ratio of NCO groups in the polyisocyanate compound expressed in mass %. 42 in the formula is the molecular weight of the NCO group.
<Formula> Number average functional group number = (number average molecular weight × NCO content (%) / 100) / 42

The mixing ratio of the polyisocyanate compound may be set in consideration of the equivalent ratio of the isocyanate groups of the polyisocyanate compound to the hydroxyl groups of the hydroxyl group-containing resin, that is, the NCO/OH ratio. The NCO/OH ratio is preferably 0.6-1.4, more preferably 0.8-1.2. With such a ratio, the effects of the present invention can be sufficiently obtained.

The topcoat material in the present invention preferably has a reactive silyl group within a range of 0.1 to 30% by weight, more preferably 0.3 to 20% by weight in terms of SiO ₂ in the solid content of the component (B). can include compounds having When the mixing ratio of the compound having a reactive silyl group is within such a range, the adhesion between the existing coating and the topcoat material coating is further increased, and peeling of the coating can be prevented. This is preferable from the point of view of maintenance of beauty and the like.

Incidentally, the SiO ₂ conversion is expressed in terms of the weight remaining as silica (SiO ₂ ) when firing at 900° C. after completely hydrolyzing a compound having an Si—O bond. In general, tetraalkoxysilanes, alkylalkoxysilanes, and the like react with water to undergo a hydrolysis reaction to form silanol, and further have the property of causing 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.

Examples of the thickening agent (C) in the topcoat material include organic bentonite, finely divided silica, surface-treated calcium carbonate, amide wax, hydrogenated castor oil wax, benzylidene sorbitol, metallic soap, polyethylene oxide, polymerized vegetable oil, and polycarboxylic acid amine. Salt etc. are mentioned. These can be used singly or in combination of two or more.

The mixing ratio of the thickener (C) is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the solid content of the resin component (B). If the mixing amount of the thickener (C) is within such a range, the topcoat material can be easily applied evenly along the unevenness of the existing wall surface, suppressing the deterioration of the existing coating, maintaining the aesthetic appearance for a long time, etc. , and the effects of the present invention can be stably obtained.

In the topcoat material, the solid content of the resin component (B) is 25 to 75% by weight in the topcoat material, preferably 35 to 70% by weight. The solid content of the resin component (B) in the topcoat material {the weight ratio of the resin component (B) in it when based on the weight of the topcoat material at the time of painting} is such a ratio, so that the existing wall surface The topcoat material can be applied evenly along the unevenness of the surface, and it is possible to form a new coating with excellent performance in terms of suppressing deterioration of the existing coating and maintaining aesthetics over the long term while making use of the uneven pattern. becomes. If the solid content of the resin component (B) is less than the above value, the state of coating of the topcoat material tends to be uneven on the existing wall surface with an uneven pattern, which may hinder the suppression of deterioration of the existing coating. . If the solid content of the resin component (B) exceeds the above value, it may be difficult to obtain a finish that takes advantage of the uneven pattern of the existing wall surface. The solid content is a value measured by the method of JIS K5601-1-2, the heating temperature is 105° C., and the heating time is 60 minutes.

The topcoat material in the present invention forms a film having visible light transmittance. As a result, it is possible to form a coating having transparency, and to obtain a finish that takes advantage of the existing coating surface color (single color, multicolor pattern, etc.). This visible light transmittance is sufficient as long as the existing coating surface can be visually recognized, and the coating may be either colorless transparent or colored transparent, and may be glossy or matte (7 minutes glossy, 5 minutes glossy, 3 minutes glossy). (including split gloss etc.). A colored transparent coating can be formed, for example, by a topcoat material containing a coloring pigment, a dye, or the like. A matte coating can be formed by a topcoat material containing, for example, extender pigments, matting agents, and the like.

The degree of visible light transmission can be indicated by visible light transmittance. Visible light transmittance is preferably 30% or more, more preferably 35 to 100%, still more preferably 40 to 95%. The visible light transmittance is a value obtained by measuring the transmittance of light with a wavelength of 580 nm for a film with a thickness of 30 μm using a spectrophotometer (transmittance is 100% when there is no film (air)). be.

In order to obtain such visible light transmittance, for example, the coloring pigment ratio in the overcoat material may be set low. The coloring pigment ratio in the overcoat material is preferably 10% by weight or less, more preferably 5% by weight or less, and still more preferably 0 to 3% by weight. An aspect in which the topcoat material does not contain a coloring pigment is also suitable.

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

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

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

Examples of the ultraviolet absorber (excluding compounds having a polymerizable unsaturated double bond) in (2) above include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and salicylate-based ultraviolet absorbers. cyanoacrylate UV absorbers, benzoate UV absorbers, malonic acid ester UV absorbers, oxalic acid anilide UV absorbers, and the like. Among these, benzophenone-based UV absorbers include, for example, 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- methoxy-2'-carboxybenzophenone, 2-hydroxy-4-stearyloxybenzophenone and the like. Examples of benzotriazole-based UV 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-benzotriazole-2 -yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl)propionate and polyethylene glycol reaction products. Examples of triazine-based UV 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)-glycidate ester reaction product, 2,4-bis" 2-Hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3-5-triazine, etc. These can be used singly or in combination of two or more. is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the solid content of the resin component (B).

As the ultraviolet shielding powder in (3) above, those having the ability to absorb and/or reflect ultraviolet rays can be used. Examples include 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, cold water stone, talc, diatomaceous earth, clay, kaolin, clay, china clay, barite powder, silica sand, Silica stone powder, white carbon, metal powder, organic resin powder and the like can be used. These can be used singly or in combination of two or more. The average particle size 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 in which visible light transmittance can be ensured.

In addition to the above components, the topcoat material in the present invention may include, if necessary, known additives such as aggregates, color grains, coloring pigments, extender pigments, dyes, gloss Erasing agent, thickener, wetting agent, dehydrating agent, leveling agent, plasticizer, fiber, anti-freezing agent, film-forming aid, preservative, anti-mold agent, anti-algae agent, antibacterial agent, dispersant, antifoaming agent , a light stabilizer, an antioxidant, an adhesion imparting agent, a low-staining agent, a hydrophilizing agent, a water repellent, a cross-linking agent, a curing accelerator, a catalyst, a solvent, and the like.

The topcoat material of the present invention can be produced by uniformly mixing the components (A), (B), (C) and, if necessary, the various components described above according to a conventional method. The form of the overcoat material can be, for example, a one-component type, a two-component type, or a multiple-component type.

The topcoat material in the present invention preferably forms a film having an elongation of 20% or more (more preferably 40% or more, still more preferably 50% or more, and particularly preferably 60% or more). In the present invention, when the elongation is within the above range, the resistance to water can be enhanced, and the effects of suppressing deterioration such as discoloration and cracking and maintaining aesthetic appearance can be further enhanced. The upper limit of elongation is preferably 300% or less, more preferably 200% or less. When the upper limit of the elongation is within such a range, it is preferable in terms of stain resistance and the like.

The elongation rate in the present invention is a value (elongation rate at 23° C.) measured by the method of "elongation test at standard time" of JIS A6909 "7.26 elongation test". However, as a test piece, one with a dry film thickness of 80 μm is used.

In the present invention, a new film is formed by applying (painting) such a topcoat material. Although the topcoat material can be applied directly to the existing wall surface, various pretreatments can be performed as necessary. Pretreatment includes, for example, removal of significantly deteriorated existing coatings, removal of contaminants by high-pressure water washing, etc., repair with putty, filler, etc., restoration of surface shape, and the like. When a new sealant is applied to an existing wall surface, it is desirable to apply the topcoat material approximately 2 to 10 days after the sealant is applied.

As the overcoat material, one or more overcoat materials satisfying the above conditions can be used. In the present invention, such a topcoat material can also be applied over. For example, one type of topcoat material may be applied multiple times, or two or more types of topcoat materials may be applied. When recoating, the coating can be dried at appropriate intervals.

A known coating tool can be used to apply the topcoat material. Examples of coating tools that can be used include sprays, rollers, and brushes. The topcoat material can be used for coating after being diluted as necessary.

The coating amount of the topcoat material is preferably 100 to 600 g/m ² , more preferably 150 to 500 g/m ² . By setting the lower limit of the coating amount of the topcoat material to the above value, the new coating is sufficiently resistant to sunlight and water, suppressing deterioration such as discoloration and cracking caused by the existing coating surface, and maintaining a beautiful appearance over the long term. It is suitable in terms of property retention and the like. By setting the upper limit of the coating amount of the topcoat material to the above value, it is possible to obtain a finish that takes advantage of the uneven pattern of the existing coating surface. In addition, when the topcoat material is applied repeatedly, it is desirable that the total coating amount is within the above range. The number of times the topcoat material is applied is preferably 1 to 3 times.

The viscosity of the topcoat material at the time of coating is preferably 0.1 to 10 Pa·s, more preferably 0.2 to 5 Pa·s. When the viscosity of the overcoat material is within such a range, the effects of the present invention can be stably obtained. The viscosity referred to herein is a value obtained by measuring the viscosity at 20 rpm (guideline value at the 4th rotation) with a BH type viscometer, and the measurement temperature is 23°C.

Drying after applying the topcoat material may be performed at room temperature (preferably 0 to 50° C., more preferably 5 to 45° C.), and can be heated if necessary.

The film thickness of the new coating formed by such a topcoat material (when recoating, the total film thickness after recoating) is preferably 30 μm or more, more preferably 50 μm or more, still more preferably 60 μm or more, and particularly preferably is greater than 65 μm, most preferably greater than or equal to 70 μm. Although the upper limit of the film thickness of the new coating is not particularly limited, it is preferably 300 μm or less, more preferably 250 μm or less, and still more preferably 200 μm or less. In addition, the film thickness in the present invention means the dry film thickness, and when one or two or more kinds of overcoat materials are overcoated, it is the total dry film thickness after overcoating.

Examples are shown below to further clarify the features of the present invention.

As topcoat materials, the following topcoat materials 1 to 17 were prepared.

(Topcoat material 1)
Polyol 1 {Non-aqueous dispersion type acrylic polyol (acrylic acid alkyl ester/methacrylic acid acrylic ester/methacrylic acid hydroxyalkyl ester copolymer dispersion liquid, component (M) 62% by weight, component (m1) 18% by weight in resin constituents , r = 0.29, hydroxyl value 40 KOH mg / g, weight average molecular weight 70000, solid content 50% by weight, medium: mineral spirit (aniline point 42 ° C.)}, ultraviolet absorber, light stabilizer, thickener (amide wax ), an antifoaming agent, and a main agent containing solvent naphtha (aniline point 13 ° C.),
Polyisocyanate 1 (1,6-diisocyanatohexane derivative, number average functionality 2.2, solid content 100% by weight), tetraalkoxysilane compound (isobutyl alcohol-modified tetramethoxysilane condensate), and mineral spirits ( ibid.) with a hardener (NCO/OH ratio 1.0).
Solid content of the resin component in the topcoat material: 45% by weight, ratio of compounds with reactive silyl groups: 3% by weight (in terms of _SiO2 ), mineral spirit ratio in all non-aqueous solvents: 80% by weight, solvent naphtha ratio: 20% by weight, ratio of thickener: 1 part by weight of solid content per 100 parts by weight of solid content of resin component, visible light transmittance: 64%, ultraviolet transmittance: 6%, elongation: 120%.

(Topcoat material 2)
Polyol 1 (same as above), Polyol 2 {fluorine-containing polyol solution, hydroxyl value 40 KOHmg/g, solid content 50% by weight, medium: mineral spirit (same as above)}, UV absorber, light stabilizer, thickener (amide wax) , an antifoaming agent, and a main agent containing solvent naphtha (same as above),
Polyisocyanate 1 (same as above), a tetraalkoxysilane compound (same as above), and a mixture with a curing agent containing mineral spirits (same as above) (NCO/OH ratio 1.0).
Polyol 1: Polyol 2 = 80:20 (solid content weight ratio),
Solid content of the resin component in the topcoat material: 45% by weight, ratio of compounds with reactive silyl groups: 3% by weight (in terms of _SiO2 ), mineral spirit ratio in all non-aqueous solvents: 80% by weight, solvent naphtha ratio: 20% by weight, ratio of thickener: 1 part by weight of solid content per 100 parts by weight of solid content of resin component, visible light transmittance: 63%, ultraviolet transmittance: 5%, elongation: 130%.

(Topcoat material 3)
a main agent comprising Polyol 1 (same as above), Polyol 2 (same as above), an ultraviolet absorber, a light stabilizer, a thickener (same as above), an antifoaming agent, and a solvent naphtha (same as above);
Polyisocyanate 1 (same as above), a tetraalkoxysilane compound (same as above), and a mixture with a curing agent containing mineral spirits (same as above) (NCO/OH ratio 1.0).
Polyol 1: Polyol 2 = 70:30 (solid content weight ratio),
Solid content of the resin component in the topcoat material: 45% by weight, ratio of compounds with reactive silyl groups: 3% by weight (in terms of _SiO2 ), mineral spirit ratio in all non-aqueous solvents: 80% by weight, solvent naphtha ratio: 20% by weight, ratio of thickener: 1 part by weight of solid content per 100 parts by weight of solid content of resin component, visible light transmittance: 63%, ultraviolet transmittance: 5%, elongation: 130%.

(Topcoat material 4)
a main agent comprising Polyol 1 (same as above), Polyol 2 (same as above), an ultraviolet absorber, a light stabilizer, a thickener (same as above), an antifoaming agent, and a solvent naphtha (same as above);
Polyisocyanate 1 (same as above), a tetraalkoxysilane compound (same as above), and a mixture with a curing agent containing mineral spirits (same as above) (NCO/OH ratio 1.0).
Polyol 1: Polyol 2 = 70:30 (solid content weight ratio),
Solid content of the resin component in the topcoat material: 38% by weight, ratio of compounds with reactive silyl groups: 3% by weight (in terms of _SiO2 ), ratio of mineral spirits in all non-aqueous solvents: 80% by weight Solvent naphtha ratio: 20% by weight, ratio of thickener: 1 part by weight of solid content per 100 parts by weight of solid content of resin component, visible light transmittance: 63%, ultraviolet transmittance: 5%, elongation: 130%.

(Topcoat material 5)
Polyol 3 {Non-aqueous dispersion type acrylic polyol (acrylic acid alkyl ester/methacrylic acid acrylic ester/methacrylic acid hydroxyalkyl ester copolymer dispersion liquid, component (M) 62% by weight, component (m1) 54% by weight in the resin constituents , r = 0.87, hydroxyl value 40 KOH mg / g, weight average molecular weight 60000, solid content 50% by weight, medium: mineral spirit (same as above)}, UV absorber, light stabilizer, thickener (same as above), antifoaming agent, and a main agent containing solvent naphtha (same as above),
Polyisocyanate 2 {1,6-diisocyanatohexane derivative, number average functionality 2.6, solid content 100% by weight}, a tetraalkoxysilane compound (same as above), and a mixture with a curing agent containing mineral spirits (same as above) (NCO/OH ratio 1.0).
Solid content of the resin component in the topcoat material: 45% by weight, ratio of compounds with reactive silyl groups: 3% by weight (in terms of _SiO2 ), mineral spirit ratio in all non-aqueous solvents: 80% by weight, solvent naphtha ratio: 20% by weight, ratio of thickener: 1 part by weight of solid content per 100 parts by weight of solid content of resin component, visible light transmittance: 62%, ultraviolet transmittance: 6%, elongation rate: 45%.

(Topcoat material 6)
a main agent comprising polyol 1 (same as above), an ultraviolet absorber, a light stabilizer, a thickener (same as above), an antifoaming agent, and a solvent naphtha (same as above);
Polyisocyanate 1 (same as above), a tetraalkoxysilane compound (same as above), and a mixture with a curing agent containing mineral spirits (same as above) (NCO/OH ratio 1.0).
Solid content of the resin component in the topcoat material: 45% by weight, ratio of compounds with reactive silyl groups: 3% by weight (in terms of _SiO2 ), mineral spirit ratio in all non-aqueous solvents: 80% by weight, solvent naphtha ratio: 20% by weight, ratio of thickener: 1 part by weight of solid content per 100 parts by weight of solid content of resin component, visible light transmittance: 65%, ultraviolet transmittance: 25%, elongation rate: 120%. In addition, the topcoat material 6 was prepared by reducing the mixing amount of the ultraviolet absorber compared to the topcoat material 1 so that the ultraviolet transmittance was the above value.

(Topcoat material 7)
a main agent comprising polyol 1 (same as above), an ultraviolet absorber, a light stabilizer, a thickener (same as above), an antifoaming agent, and a solvent naphtha (same as above);
Polyisocyanate 1 (same as above), a tetraalkoxysilane compound (same as above), and a mixture with a curing agent containing mineral spirits (same as above) (NCO/OH ratio 1.0).
Solid content of the resin component in the topcoat material: 45% by weight, ratio of compounds with reactive silyl groups: 3% by weight (in terms of _SiO2 ), mineral spirit ratio in all non-aqueous solvents: 80% by weight, solvent naphtha ratio: 20% by weight, ratio of thickener: 0.1 part by weight of solid content per 100 parts by weight of solid content of resin component, visible light transmittance: 64%, ultraviolet transmittance: 6%, elongation: 120%.

(Topcoat material 8)
a main agent comprising Polyol 3 (same as above), Polyol 2 (same as above), an ultraviolet absorber, a light stabilizer, a thickener (same as above), an antifoaming agent, and a solvent naphtha (same as above);
A mixture with a curing agent containing Polyisocyanate 2 (same as above), a tetraalkoxysilane compound (same as above), and mineral spirits (same as above) (NCO/OH ratio 1.0).
Polyol 3: Polyol 2 = 70:30 (solid content weight ratio),
Solid content of the resin component in the topcoat material: 45% by weight, ratio of compounds with reactive silyl groups: 3% by weight (in terms of _SiO2 ), mineral spirit ratio in all non-aqueous solvents: 80% by weight, solvent naphtha ratio: 20% by weight, ratio of thickener: 1 part by weight of solid content per 100 parts by weight of solid content of resin component, visible light transmittance: 62%, ultraviolet transmittance: 6%, elongation rate: 45%.

(Topcoat material 9)
a main agent comprising Polyol 1 (same as above), Polyol 2 (same as above), an ultraviolet absorber, a light stabilizer, a thickener (same as above), an antifoaming agent, and a solvent naphtha (same as above);
Polyisocyanate 1 (same as above), a tetraalkoxysilane compound (same as above), and a mixture with a curing agent containing mineral spirits (same as above) (NCO/OH ratio 1.0).
Polyol 1: Polyol 2 = 70:30 (solid content weight ratio),
Solid content of the resin component in the topcoat material: 45% by weight, ratio of compounds with reactive silyl groups: 3% by weight (in terms of _SiO2 ), mineral spirit ratio in all non-aqueous solvents: 80% by weight, solvent naphtha ratio: 20% by weight, ratio of thickener: 1 part by weight of solid content per 100 parts by weight of solid content of resin component, visible light transmittance: 64%, ultraviolet transmittance: 25%, elongation rate: 130%. In addition, the topcoat material 9 was prepared by reducing the mixing amount of the ultraviolet absorber compared to the topcoat material 4 so that the ultraviolet transmittance was the above value.

(Topcoat material 10)
a main agent comprising Polyol 1 (same as above), Polyol 2 (same as above), an ultraviolet absorber, a light stabilizer, a thickener (same as above), an antifoaming agent, and a solvent naphtha (same as above);
Polyisocyanate 1 (same as above), a tetraalkoxysilane compound (same as above), and a mixture with a curing agent containing mineral spirits (same as above) (NCO/OH ratio 1.0).
Polyol 1: Polyol 2 = 70:30 (solid content weight ratio),
Solid content of the resin component in the topcoat material: 45% by weight, ratio of compounds with reactive silyl groups: 3% by weight (in terms of _SiO2 ), mineral spirit ratio in all non-aqueous solvents: 80% by weight, solvent naphtha ratio: 20% by weight, ratio of thickener: 0.1 part by weight of solid content per 100 parts by weight of solid content of resin component, visible light transmittance: 64%, ultraviolet transmittance: 6%, elongation rate: 130%.

(Topcoat material 11)
Polyol 4 {Soluble acrylic polyol (acrylic acid alkyl ester/methacrylic acid acrylic ester/methacrylic acid hydroxyalkyl ester copolymer solution, component (M) 62% by weight, component (m1) 18% by weight, r = 0.29,
Hydroxyl value 50 KOH mg/g, weight average molecular weight 20000, solid content 50% by weight, medium: mineral spirit (same as above)}, polyol 2 (same as above), UV absorber, light stabilizer, thickener (same as above), antifoaming agent , and a main agent containing solvent naphtha (same as above),
Polyisocyanate 1 (same as above), a tetraalkoxysilane compound (same as above), and a mixture with a curing agent containing mineral spirits (same as above) (NCO/OH ratio 1.0).
Polyol 1: Polyol 2 = 70:30 (solid content weight ratio),
Solid content of the resin component in the topcoat material: 45% by weight, ratio of compounds with reactive silyl groups: 3% by weight (in terms of _SiO2 ), mineral spirit ratio in all non-aqueous solvents: 80% by weight, solvent naphtha ratio: 20% by weight, ratio of thickener: 1 part by weight of solid content per 100 parts by weight of solid content of resin component, visible light transmittance: 64%, ultraviolet transmittance: 6%, elongation: 120%.

(Topcoat material 12)
a main agent comprising Polyol 1 (same as above), Polyol 2 (same as above), an ultraviolet absorber, a light stabilizer, a thickener (same as above), an antifoaming agent, and a solvent naphtha (same as above);
Polyisocyanate 1 (same as above), a tetraalkoxysilane compound (same as above), and a mixture with a curing agent containing mineral spirits (same as above) (NCO/OH ratio 1.0).
Polyol 1: Polyol 2 = 50:50 (solid content weight ratio),
Solid content of the resin component in the topcoat material: 45% by weight, ratio of compounds with reactive silyl groups: 3% by weight (in terms of _SiO2 ), mineral spirit ratio in all non-aqueous solvents: 80% by weight, solvent naphtha ratio: 20% by weight, ratio of thickener: 1 part by weight of solid content per 100 parts by weight of solid content of resin component, visible light transmittance: 62%, ultraviolet transmittance: 5%, elongation rate: 130%.

(Topcoat material 13)
a main agent comprising Polyol 1 (same as above), Polyol 2 (same as above), an ultraviolet absorber, a light stabilizer, a thickener (same as above), an antifoaming agent, and a solvent naphtha (same as above);
Polyisocyanate 1 (same as above), a tetraalkoxysilane compound (same as above), and a mixture with a curing agent containing mineral spirits (same as above) (NCO/OH ratio 1.0).
Polyol 1: Polyol 2 = 30:70 (solid content weight ratio),
Solid content of the resin component in the topcoat material: 45% by weight, ratio of compounds with reactive silyl groups: 3% by weight (in terms of _SiO2 ), mineral spirit ratio in all non-aqueous solvents: 80% by weight, solvent naphtha ratio: 20% by weight, ratio of thickener: 1 part by weight of solid content per 100 parts by weight of solid content of resin component, visible light transmittance: 61%, ultraviolet transmittance: 5%, elongation rate: 140%.

(Topcoat material 14)
a main agent comprising Polyol 1 (same as above), Polyol 2 (same as above), an ultraviolet absorber, a light stabilizer, a thickener (same as above), an antifoaming agent, and a solvent naphtha (same as above);
Polyisocyanate 1 (same as above), a tetraalkoxysilane compound (same as above), and a mixture with a curing agent containing mineral spirits (same as above) (NCO/OH ratio 1.0).
Polyol 1: Polyol 2 = 99.2: 0.8 (solid content weight ratio),
Solid content of the resin component in the topcoat material: 45% by weight, ratio of compounds with reactive silyl groups: 3% by weight (in terms of _SiO2 ), mineral spirit ratio in all non-aqueous solvents: 80% by weight, solvent naphtha ratio: 20% by weight, ratio of thickener: 1 part by weight of solid content per 100 parts by weight of solid content of resin component, visible light transmittance: 64%, ultraviolet transmittance: 5%, elongation: 120%.

(Topcoat material 15)
a main agent comprising polyol 1 (same as above), an ultraviolet absorber, a light stabilizer, a thickener (same as above), an antifoaming agent, and a solvent naphtha (same as above);
Polyisocyanate 1 (same as above), a tetraalkoxysilane compound (same as above), and a mixture with a curing agent containing mineral spirits (same as above) (NCO/OH ratio 1.0).
Solid content of the resin component in the topcoat material: 22% by weight, ratio of compounds with reactive silyl groups: 3% by weight (in terms of _SiO2 ), mineral spirit ratio in all non-aqueous solvents: 80% by weight, solvent naphtha ratio: 20% by weight, ratio of thickener: 1 part by weight of solid content per 100 parts by weight of solid content of resin component, visible light transmittance: 64%, ultraviolet transmittance: 6%, elongation: 120%.

(Topcoat material 16)
a main agent comprising polyol 4 (same as above), an ultraviolet absorber, a light stabilizer, a thickener (same as above), an antifoaming agent, and a solvent naphtha (same as above);
Polyisocyanate 1 (same as above) and a mixture with a curing agent containing mineral spirits (same as above) (NCO/OH ratio 1.0).
Solid content of the resin component in the topcoat material: 45% by weight, ratio of compounds with reactive silyl groups: 0% by weight (in terms of _SiO2 ), ratio of mineral spirits in all non-aqueous solvents: 80% by weight Solvent naphtha ratio: 20% by weight, ratio of thickener: 1 part by weight of solid content per 100 parts by weight of solid content of resin component, visible light transmittance: 65%, ultraviolet transmittance: 6%, elongation rate: 120%.

(Topcoat material 17)
Polyol 4 (same as above), UV absorber, light stabilizer, thickener (same as above), defoamer and mixture with solvent naphtha (same as above) and mineral spirits (same as above).
Solid content of the resin component in the topcoat material: 45% by weight, ratio of compounds with reactive silyl groups: 0% by weight (in terms of _SiO2 ), ratio of mineral spirits in all non-aqueous solvents: 80% by weight Solvent naphtha ratio: 20% by weight, ratio of thickener: 1 part by weight of solid content per 100 parts by weight of solid content of resin component, visible light transmittance: 65%, ultraviolet transmittance: 6%, elongation rate: 60%.

○ Preparation of test specimen As an existing wall surface, a gray ceramic siding boat that has deteriorated due to outdoor exposure (the surface has tile joint-like protrusions and recesses (joints), the protrusions have an irregular uneven pattern, and the outermost layer (having an inorganic clear film as a coating film) was prepared. On the entire surface of the existing wall surface, the topcoat material was spray-coated at a coating amount of 110 g/m ² (30 g/m ² in Examples 15 and 16), dried for 2 hours, and then coated again at a coating amount of 110 g/m ² (30 g/m 2 in Examples 15 and 16). In Examples 15 and 16, test specimens were prepared by spray coating at 30 g/m ² ) and drying and curing for 7 days. All the coating and curing steps were carried out under standard conditions (temperature 23°C, relative humidity 50%).

○ Exam I
First, as test I, the following tests I-1 to I-4 were performed.

(Test I-1)
After 14 days of immersion in water, the test piece prepared by the above method was cross-cut with a cutter knife on each part of the coating of the uneven pattern, and the adhesion was evaluated by sticking a tape to the cross-cut part and peeling it off. Evaluation was performed as "A" when no peeling was observed, "B" when generally good but partial peeling was observed, and "C" when a lot of peeling was observed. rice field.

(Test I-2)
After exposing the specimen prepared by the above method to an accelerated weather resistance tester (Metal Weather; manufactured by Daipla Wintes Co., Ltd.) for 500 hours, changes in the appearance of the specimen surface (gloss, color, floating, peeling, state of cracks) was observed. The evaluation is performed by comparing the change in appearance with that of the test piece before exposure, with three levels of "A: No change" and "C: Decreased gloss, discoloration, floating, peeling or crack progress"(excellent;A>B>C; inferior).

(Test I-3)
After the above test I-2, exposure by an accelerated weather resistance tester was performed for an additional 500 hours (total of 1000 hours), and changes in the appearance of the surface of the specimen (gloss, color, floating, peeling, cracking) were observed. The evaluation is performed by comparing the change in appearance with that of the test piece before exposure, with three levels of "A: No change" and "C: Decreased gloss, discoloration, floating, peeling or crack progress"(excellent;A>B>C; inferior).

(Test I-4)
The specimen prepared by the above method was exposed to the outdoors for 3 months, and the appearance change due to dirt on the surface of the specimen was observed. >B>C; inferior).

(Results of test I)
The results of Test I are shown in Tables 1-3. In Examples 1 to 16, the new coating formed from each topcoat material made it possible to obtain a finish that took advantage of the uneven pattern and color pattern of the existing wall surface, and good results were obtained in Tests I-1 to I-4. I was able to get

○ Exam II
After the above test I-3, exposure by an accelerated weather resistance tester was further performed for 500 hours (total of 1500 hours), and changes in appearance (gloss, color, floating, peeling, and cracking) of the specimen surface were observed. The evaluation is performed by comparing the change in appearance with that of the test piece before exposure, with three levels of "A: No change" and "C: Decreased gloss, discoloration, floating, peeling or crack progress"(excellent;A>B>C; inferior).

(Results of Test II)
The results of Test II are shown in Table 4. Examples 2-4, 8-13 and 15 also gave good results in test II.

Claims (3)

A film forming method for applying a topcoat material to an existing wall surface that has deteriorated over time,
The existing wall surface has an uneven pattern on the surface and is provided with an existing coating,
The topcoat material contains a non-aqueous solvent (A), a resin component (B), and a thickener (C),
The non-aqueous solvent (A) contains a non-aqueous solvent having an aniline point of 12 to 70 ° C.,
The resin component (B) is composed of one or more compounds, at least one of which is a compound having a reactive silyl group,
The solid content of the resin component (B) is 25 to 75% by weight in the topcoat material,
A method of forming a film, wherein the topcoat material is transparent to visible light and forms a film having an ultraviolet transmittance of 30% or less. The resin component (B) consists of one or more compounds,
2. The method of forming a film according to claim 1, wherein at least one of said compounds is a resin having a weight average molecular weight of 10,000 to 150,000. 3. The film forming method according to claim 1, wherein the existing wall surface has an uneven pattern on the surface and is composed of a plurality of plate-like wall materials provided with the existing film.