JP2009028712A - Coated body and its forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To hardly stain and easily remove stains even in staining in a coated body having a convex-concave pattern. <P>SOLUTION: A coated film is applied on the surface of coated body having a convex-concave pattern which is made of a coating material in which a synthetic resin emulsion (A) where an acrylic resin with an alkyl (meth)acrylic acid ester as a main unit component and a silicone resin with a siloxane compound as a main unit component coexist in an emulsion particles in a weight ratio of 99:1 to 30:70, and in which a particle body (B) with an average diameter of 0.5-500 μm and with an oil absorption of 60 ml/100 g or lower is applied as an essential component and in which the pigment volume concentration of a particle body (B) is 10-90%. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel coated body and a method for forming the same.

2. Description of the Related Art Conventionally, in a wall surface of a building or the like, as a means for improving the aesthetics, a method of directly coating the wall surface or affixing a pre-painted wall covering to the wall surface has been adopted. In such a method, it is possible to select a desired color, and it is possible to express a wide variety of aesthetics by providing a surface uneven pattern.
As a method for providing such a concavo-convex pattern, for example, in Patent Document 1, a base wallpaper for forming a concavo-convex pattern is attached to a wall surface using an adhesive, and after the adhesive is dried, a paint is applied to the surface of the wallpaper. A method of painting is described. Patent Document 2 describes a method in which after a paint is applied to a base material, a brush-like uneven pattern is imparted to the surface of the coating film in a semi-dry state and dried. Patent Document 3 describes a method in which a synthetic resin emulsion-based paint is applied to a substrate, the coating film is gelled, a pattern is applied to the surface immediately after gelation, and then dried. Patent Document 4 describes a method of applying an aqueous emulsion resin on a substrate to form an aqueous emulsion resin layer, and further embossing and the like.

  According to the method of the above-mentioned patent document, various uneven patterns can be provided. However, such a concavo-convex pattern is difficult to remove once dirt is attached to the surface, and may not be easily removed. In particular, dirt tends to accumulate in the concave and convex portions. Such dirt is detrimental to aesthetics, but the above-mentioned patent document hardly considers adhesion and removal of dirt.

  The present invention has been made in view of the above problems, and it is an object of the present invention to make a coated body having a concavo-convex pattern difficult to get dirty, and to be easily removed even when dirty. Is.

Japanese Patent Laid-Open No. 2-167953 JP-A-6-173411 JP-A-6-285422 JP-A-8-332443

  As a result of intensive studies to achieve the above object, the present inventor has conceived that a coating film made of a specific coating material is formed on a base having a concavo-convex pattern, and has completed the present invention. .

  That is, the present invention has the following characteristics.

1. It is a painted body having a concavo-convex pattern, at least on its surface,
Synthesis in which emulsion resin contains acrylic resin having (meth) acrylic acid alkyl ester as main monomer component and silicone resin having siloxane compound as main monomer component in a weight ratio of 99: 1 to 30:70. Resin emulsion (A), an average particle diameter of 0.5 to 500 μm, an oil absorption of 60 ml / 100 g or less powder (B) as an essential component, the pigment volume concentration of the powder (B) is 10 to 90% A coated body characterized in that a coating film is formed by a certain covering material.
2. The synthetic resin emulsion (A) in the coating material is one in which the silicone resin is present at least in the emulsion particle surface layer. The painted body described.
3. The synthetic resin emulsion (A) in the covering material is a multilayer structure type synthetic resin emulsion having an outer layer containing the silicone resin and an inner layer containing the acrylic resin. Or 2. The painted body described.
4). The synthetic resin emulsion (A) in the covering material is a multilayer structure type synthetic resin emulsion having an outer layer in which the acrylic resin and the silicone resin are mixed, and an inner layer containing the acrylic resin. ~ 3. Painted body according to any one of
5). For the groundwork with an uneven pattern,
Synthesis in which emulsion resin contains acrylic resin having (meth) acrylic acid alkyl ester as main monomer component and silicone resin having siloxane compound as main monomer component in a weight ratio of 99: 1 to 30:70. Resin emulsion (A), an average particle diameter of 0.5 to 500 μm, an oil absorption of 60 ml / 100 g or less powder (B) as an essential component, the pigment volume concentration of the powder (B) is 10 to 90% A certain covering material
A method for forming a coated body, wherein the coating is applied so that the uneven pattern is maintained.
6). For the groundwork
Synthesis in which emulsion resin contains acrylic resin having (meth) acrylic acid alkyl ester as main monomer component and silicone resin having siloxane compound as main monomer component in a weight ratio of 99: 1 to 30:70. Resin emulsion (A), an average particle diameter of 0.5 to 500 μm, an oil absorption of 60 ml / 100 g or less powder (B) as an essential component, the pigment volume concentration of the powder (B) is 10 to 90% Apply a certain covering material,
A method for forming a coated body, comprising providing an uneven pattern on a coating film surface of the covering material.

  ADVANTAGE OF THE INVENTION According to this invention, in the coating body which has an uneven | corrugated pattern, adhesion of the stain | pollution | contamination to the surface can be suppressed. Further, even if dirt is attached, it can be easily removed. Therefore, in the present invention, the initial aesthetics can be maintained for a long time.

  Hereinafter, the best mode for carrying out the present invention will be described.

[Coating material]
First, the covering material used in the present invention will be described.
The synthetic resin emulsion (A) (hereinafter referred to as “component (A)”) in the coating material of the present invention has an acrylic resin derived from (meth) acrylic acid alkyl ester and a silicone resin derived from a siloxane compound in the emulsion particles. It is a mixture. The form of the acrylic resin and the silicone resin in the component (A) is not particularly limited, and may be a uniformly mixed form, but a form separated from each other by a sea-island structure or the like is preferable.
The acrylic resin derived from the (meth) acrylic acid alkyl ester in the component (A) contains (meth) acrylic acid alkyl ester as the main monomer component (at least 30% by weight, preferably 40% based on the total monomers constituting the acrylic resin). Weight percent or more, more preferably 50 weight percent or more, and still more preferably 70 weight percent or more). In addition, the silicone resin derived from the siloxane compound in the component (A) contains 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more of the siloxane compound with respect to the main monomer component (all monomers constituting the silicone resin). Weight percent or more).

  The weight ratio of the acrylic resin and the silicone resin in the component (A) is usually 99: 1 to 30:70, preferably 97: 3 to 40:60, more preferably 95: 5 to 50:50. By mixing both components at such a ratio, it is possible to obtain a coating material having excellent antifouling properties, water repellency, film-forming properties, crack prevention properties, and the like.

  (A) The acrylic resin which comprises a component is a polymer which has (meth) acrylic-acid alkylester as a main component, and copolymerizes another monomer as needed. Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate. , N-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (Meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and the like. The amount of the (meth) acrylic acid alkyl ester used is usually 30% by weight or more, preferably 40 to 99.9% by weight, more preferably 50 to 99.9%, based on all monomers constituting the component (A). 5% by weight, more preferably 70-99.5% by weight.

  Examples of other monomers include carboxyl group-containing monomers, amino group-containing monomers, pyridine monomers, hydroxyl group-containing monomers, nitrile group-containing monomers, amide group-containing monomers, epoxy group-containing monomers, carbonyl group-containing monomers, and alkoxysilyl group-containing monomers. And aromatic monomers. The amount of these monomers to be used is generally 0.1 to 60% by weight, preferably 0.5 to 50% by weight, more preferably 0.5 to 30% by weight, based on all monomers constituting the component (A). .

  Among these, when a carboxyl group-containing monomer is copolymerized to obtain a carboxyl group-containing acrylic resin, the stability of the component (A) can be increased, and a compound capable of reacting with a carboxyl group is added separately. Therefore, various physical properties of the coating film can be improved. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, maleic acid or a monoalkyl ester thereof, itaconic acid or a monoalkyl ester thereof, fumaric acid or a monoalkyl ester thereof. Among these, at least one selected from acrylic acid and methacrylic acid is particularly preferable. The usage-amount of a carboxyl group-containing monomer is 0.1 to 40 weight% normally with respect to all the monomers which comprise (A) component, Preferably it is 0.5 to 20 weight%.

The silicone resin in component (A) is obtained by polymerizing a siloxane compound. Examples of the siloxane compound include those having a structural unit represented by a general formula R _n SiO _{(4-n) / 2} (wherein R is a hydrocarbon group, n = 0 to 3). Examples of such a compound include a linear siloxane compound, a branched siloxane compound, a cyclic siloxane compound, and the like, among which a cyclic siloxane compound is preferable. Examples of the cyclic siloxane compound include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like. When such a cyclic siloxane compound is polymerized, a linear siloxane compound, a branched siloxane compound, an alkoxysilane compound, or the like can be used, and a polymerization catalyst can be appropriately used. Of these, as the alkoxysilane compound, a silane compound having one or more alkoxyl groups in the molecule can be used. For example, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, γ- Silane coupling agents such as (meth) acryloyloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane can be used. When the cyclic siloxane compound is polymerized, it is possible to chemically bond the silicone resin and the acrylic resin by using such an alkoxysilane compound in combination, which is advantageous in improving the physical properties of the coating film such as water resistance. . The average molecular weight of the silicone resin is usually 10,000 or more, preferably 50,000 or more.

The component (A) in the present invention is particularly preferably a synthetic resin emulsion in which an acrylic resin and a silicone resin are mixed as described above, and at least the emulsion particle surface layer includes the silicone resin. As such component (A), a multilayer structure type synthetic resin emulsion having an outer layer containing a silicone resin and an inner layer containing an acrylic resin, an outer layer in which an acrylic resin and a silicone resin are mixed, and a multilayer having an inner layer containing an acrylic resin Examples include structural synthetic resin emulsions. If such a synthetic resin emulsion is used, a more remarkable effect can be obtained in terms of antifouling performance, water repellency and the like.
The component (A) is a synthetic resin emulsion in which an acrylic resin and a silicone resin are mixed as described above, and has an outer layer in which an acrylic resin and a silicone resin are mixed, and an inner layer containing the acrylic resin, and the acrylic resin in the outer layer. A multilayer structure type synthetic resin emulsion (A-1) (hereinafter referred to as “component (A-1)”) in which the glass transition temperature of the acrylic resin in the inner layer is set lower than the glass transition temperature of the inner layer is preferred. By using such a synthetic resin emulsion, it is possible to obtain more remarkable effects in terms of anti-contamination performance, water repellency, and the like, and it is also possible to enhance coating film performance such as crack prevention. The weight ratio of the outer layer to the inner layer is usually 80:20 to 20:80, preferably 70:30 to 30:70.

Such component (A-1) can be obtained, for example, by a method of synthesizing an acrylic resin constituting the inner layer by emulsion polymerization and then synthesizing an acrylic resin and a silicone resin constituting the outer layer by emulsion polymerization. In the component (A-1), the silicone resin as described above may be contained as a resin constituting the inner layer. By including a silicone resin in the inner layer, it is possible to enhance crack prevention properties and the like.
Here, the glass transition temperature (hereinafter referred to as “Tg”) of the acrylic resin constituting the inner layer may be usually set to −60 to 20 ° C. (preferably −50 to 10 ° C.). The Tg of the acrylic resin constituting the outer layer is usually 20 to 100 ° C. (preferably 30 to 90 ° C.). When the Tg of the acrylic resin in each layer is within such a range, the above-described effects can be stably obtained. Note that Tg in the present invention is a value obtained by the Fox calculation formula.

  In the present invention, when the carboxyl group-containing acrylic resin is contained in the component (A), by adding a compound capable of reacting with the carboxyl group separately, contamination prevention, blistering prevention, peeling prevention, washing resistance, etc. Can enhance the effect. Furthermore, the tackiness of the coating film surface can be suppressed. Examples of such a compound include compounds having one or more functional groups selected from a carbodiimide group, an epoxy group, an aziridine group, an oxazoline group, and the like. Among these, in the present invention, a reactive compound having an epoxy group is particularly suitable.

  Examples of the reactive compound having an epoxy group include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol poly Examples thereof include glycidyl ether, diglycerol polyglycidyl ether, polyhydroxyalkane polyglycidyl ether, and sorbitol polyglycidyl ether. In addition, a water-soluble resin or emulsion made of a polymer (homopolymer or copolymer) of an epoxy group-containing monomer can also be used. The mixing amount of such a compound is usually 0.1 to 50 parts by weight, preferably 0.3 to 20 parts by weight with respect to 100 parts by weight of the resin solid content of the component (A).

  In the coating material of the present invention, the component (A) is used as a binder, but a binder other than the component (A) can be used in combination with the component (A). As such a binder, for example, synthetic resin emulsions other than the component (A), various water-soluble resins, and the like can be used. These may have crosslinking reactivity. Usable types of resin include, for example, cellulose, polyvinyl alcohol, vinyl acetate resin, alkyd resin, vinyl chloride resin, epoxy resin, silicone resin, acrylic resin, urethane resin, acrylic silicon resin, fluorine resin, or the like. A composite system etc. can be mentioned. In the present invention, by using the component (A) in combination with other binders, effects such as improvement in water repellency over time can be obtained. The mixing ratio of the component (A) and the other binder may be about 95: 5 to 20:80 (preferably 90:10 to 30:70) in terms of solid content.

  When a crosslinking reaction type synthetic resin emulsion is used as a binder other than the component (A), physical properties such as contamination prevention and water resistance can be further enhanced. Examples of the crosslinking reaction in such a crosslinking reaction type synthetic resin emulsion include hydroxyl group and isocyanate group, carbonyl group and hydrazide group, carboxyl group and metal ion, epoxy group and amino group, epoxy group and carboxyl group, epoxy group and hydrazide group. And a combination of a carboxyl group and a carbodiimide, a carboxyl group and an oxazoline, an alkoxysilyl group, or the like. As the crosslinking reaction type emulsion, a crosslinking reaction as exemplified herein may be generated in the emulsion particles, or a crosslinking reaction may be generated between the emulsion particles and the crosslinking agent. When using a crosslinking reaction type synthetic resin emulsion, the mixing ratio of the component (A) and the crosslinking reaction type synthetic resin emulsion is usually 95: 5 to 20:80 (preferably 90:10 to 30:70) in terms of solid content. It is desirable to set the degree. In the present invention, such a compound capable of reacting with a carboxyl group and such a crosslinkable synthetic resin emulsion can be used in combination.

  In the coating material of the present invention, in addition to the component (A) described above, the powder (B) (hereinafter referred to as “component (B)”) having an average particle size of 0.5 to 500 μm and an oil absorption of 60 ml / 100 g or less is an essential component. The component (B) is blended within a range where the pigment volume concentration is 10 to 90%. In the present invention, by blending the component (B) in this way, a fine uneven structure is imparted to the surface of the formed coating film, and the contact area when water droplets contact the coating film can be reduced. Excellent anti-contamination effect, water repellent effect, etc. are obtained.

  The range of the suitable average particle diameter in (B) component is 1-200 micrometers (more preferably 2-100 micrometers, More preferably, 3-80 micrometers). When the average particle size of the component (B) is outside the above range, it is difficult to obtain sufficient effects in terms of antifouling performance, water repellency and the like. Specifically, when the average particle size of the component (B) is too large, the surface of the coating film becomes too rough, and water or the like may enter the coating film. When the average particle size is too small, it becomes difficult to form a fine concavo-convex structure that contributes to improving water repellency. In addition, the average particle diameter of (B) component is based on observation with a transmission electron microscope, and is a value obtained by determining the particle diameter distribution (number basis) when the equivalent circle diameter of each particle is the diameter. is there.

  The oil absorption amount of the component (B) is 60 ml / 100 g or less, preferably 40 ml / 100 g or less, more preferably 20 ml / 100 g or less. When the oil absorption amount of the component (B) exceeds the above range, a large amount of dispersant is required to disperse the component (B), and the water repellency effect will be hindered. The oil absorption amount (ml / 100 g) is a value obtained by the method defined in JIS K 5101-13-2: 2004, and is expressed in ml of boiled linseed oil with respect to 100 g of the granular material. is there.

  As (B) component in this invention, as long as the said physical property is satisfy | filled, the material is not specifically limited, Various powder bodies can be used. For example, heavy calcium carbonate, kaolin, clay, porcelain clay, china clay, talc, barite powder, barium sulfate, barium carbonate, magnesium carbonate, silica powder, aluminum hydroxide and the like can be mentioned. In addition, marble, granite, serpentine, granite, fluorite, cryolite, feldspar, limestone, quartzite, quartz sand, crushed stone, mica, siliceous shale, and pulverized products thereof, ceramic pulverized product, ceramic pulverized product, glass pulverized product Products, resin pulverized products, rubber particles, plastic pieces, metal particles, etc., and those whose surfaces are colored and coated can also be used. In the present invention, as the component (B), two or more kinds of granular materials having different average particle diameters can be used in combination. In the present invention, it is particularly preferable that silica powder is contained as the component (B). The content of the silica powder in the component (B) can be 30% by volume or more, preferably 40% by volume or more and less than 80% by volume, and more preferably 50% by volume or more and less than 70% by volume.

Further, the component (B) is preferably not spherical, and preferably contains non-spherical materials such as granular, angular, needle-like, irregular, and flake-like. . In the present invention, the component (B) preferably contains at least a scaly product. Specific examples of the flake shaped material include talc, mica, clay and the like. The content of the flakes in the component (B) can be 10% by volume or more, preferably 20% by volume or more and less than 60% by volume, and more preferably 30% by volume or more and less than 50% by volume. More preferred.
In the present invention, by using such a component (B), the anti-contamination property and the like can be further enhanced.

  The component (B) in the coating material of the present invention is mixed within a range in which the pigment volume concentration is 10 to 90% (preferably 20 to 70%, more preferably 25 to 55%). When the pigment volume concentration of the component (B) is too small, it is difficult to obtain a sufficient anti-contamination effect, a water repellent effect and the like, and it may be difficult to obtain a stable paintability. When the pigment volume concentration of the component (B) is too large, cracks are likely to occur in the coating film, and physical properties such as antifouling properties and waterproofness may be insufficient. In addition, the pigment volume concentration of (B) component in this invention is a volume percentage of (B) component contained in a dry coating film, and is calculated from the compounding quantity of the binder which comprises a coating material, and (B) component. This is the required value.

  In the present invention, if it is within the range in which the contamination prevention effect, water repellency effect and the like due to the above-mentioned components are not significantly impaired, the powder component other than the above-mentioned component (B), for example, an inorganic color pigment, an organic color pigment, etc. Can also be mixed. By mixing such a color pigment, the coating material can be toned in a desired hue, and the antifouling performance, water repellency, etc. of the formed coating film can be enhanced. The average particle diameter of the color pigment is usually less than 0.5 μm (preferably 0.4 μm or less).

  In the present invention, the pigment volume concentration of the entire coating material is desirably set to 40 to 90% (preferably 45 to 70%, more preferably 45 to 60%). By setting the pigment volume concentration of the entire coating material within such a range, the effects of the present invention can be stably obtained. In addition, the pigment volume concentration of the whole coating material is the volume percentage of the whole granular material contained in the dry coating film, and is a value obtained by calculation from the blending amount of the binder and the granular material constituting the coating material. .

  In addition, in the coating material, unless the effects of the present invention are significantly impaired, for example, a thickener, a film-forming aid, a leveling agent, a wetting agent, a plasticizer, an antifreezing agent, a pH adjusting agent, a preservative, A glaze, an anti-algae agent, an antibacterial agent, a dispersant, an antifoaming agent, an adsorbent, an aggregate, a fiber, a water repellent, a cross-linking agent, an ultraviolet absorber, an antioxidant, a catalyst, and the like can also be mixed. The coating material of this invention can be manufactured by mixing the above components uniformly by a conventional method.

[Coated body]
The coated body of the present invention has a concavo-convex pattern, and has a coating film of the above coating material on at least the surface thereof. Such a painted body is mainly applicable to the wall surface of a building.

  The uneven pattern in the coated body of the present invention is a surface pattern having a height difference of about 0.2 to 5 mm. Examples of such concavo-convex patterns include various patterns such as sand wall shape, yuzu skin shape, fiber wall shape, ripple shape, stucco shape, uneven shape, lunar surface shape, comb-drawn shape, insect-like shape, lattice shape, and stripe shape. In addition, there are graphic patterns and geometric patterns designed with animals and plants, objects, characters, etc.

  As the base of the painted body, various base materials applicable to buildings and the like can be used. For example, gypsum board, plywood, concrete, mortar, porcelain tile, fiber-mixed cement board, cement calcium silicate board, slag cement pearlite board, An ALC board, a siding board, an extrusion molding board, a steel plate, a plastic board etc. are mentioned. Moreover, base materials, such as a woven fabric, a nonwoven fabric, ceramic paper, a synthetic paper, a glass cloth, a mesh, and a wallpaper, can also be used for a foundation | substrate, and it can also be used in combination of a multiple types of base material. The surface of these base materials may have been subjected to some surface treatment (for example, a sealer, a surfacer, a filler, a putty, etc.), or may have already been formed with a coating film.

  The coated body of the present invention can be formed, for example, by applying the covering material to a ground that constitutes a wall surface of a building or the like, and is formed by applying the covering material to a ground that can be distributed ( Manufacturing). In the latter case, the obtained coated body may be carried into the construction site and applied to the wall surface.

The coated body of the present invention can be formed, for example, by the following method.
(1) A method of applying the coating material to a base having a concavo-convex pattern so that the concavo-convex pattern is retained.
(2) A method in which the coating material is applied to the base and a concavo-convex pattern is imparted to the coating film surface of the coating material.

In said (1), the base | substrate which has an uneven | corrugated pattern is made into a coating object. Specific examples of the base include, for example, a base material itself having a concavo-convex pattern, a coating film having a concavo-convex pattern, a laminate of wallpaper and the like on a base material, and the like.
Of these, the substrate itself having a concavo-convex pattern can be obtained by performing mold forming, embossing, or the like at the time of manufacturing the substrate.
A film having a concavo-convex pattern laminated on a substrate can be obtained by forming a concavo-convex pattern on the surface of the coating film when the coating material is applied to the substrate or before the coating film is dried. it can. Examples of the coating material used in this case include JIS A6909 thin finish coating material, thick finish coating material, and stone finish finishing coating material. In such a coating material, various uneven patterns can be formed by performing coating by appropriately setting a coating tool or viscosity at the time of coating. Moreover, various uneven | corrugated patterns can also be formed by processing the coating-film surface with a design roller, a trowel, a brush, a comb, a spatula etc. before drying of a coating film.
On the other hand, various wallpaper such as a paint base cloth (painted base wallpaper) can be used as the wallpaper having the uneven pattern.

In the above (1), the covering material is applied so that the concavo-convex pattern of the base is maintained. Here, the coating may be performed so that a part or all of the concavo-convex pattern derived from the base can be recognized after coating the coating material. The coating amount of the coating material is usually about 0.1 to 0.6 kg / m ² , preferably about 0.2 to 0.5 kg / m ² .

  In the above (1), a coating material can be applied after applying an undercoat material such as a sealer or a surfacer to a coating film or wallpaper having an uneven pattern. In particular, in the case where a coating film or wallpaper to be painted is deteriorated over time, physical properties such as adhesion can be enhanced by using a primer. If such a coating film and a wallpaper contain a plasticizer etc., transfer to the coating-film surface of a plasticizer etc. can be suppressed and a stain | pollution | contamination prevention effect can also be improved.

  As the binder in the primer, various binders such as water-soluble resins, water-dispersible resins (resin emulsions), solvent-soluble resins, solvent-free resins, non-water-dispersible resins, or a combination of these. Materials etc. can be used. In the present invention, water-soluble resins and / or water-dispersible resins are suitable. These may have crosslinking reactivity. Further, the form of the binding material is not particularly limited, and may be either one liquid type or two liquid type. Examples of the types of resins that can be used include vinyl acetate resins, vinyl chloride resins, epoxy resins, silicone resins, acrylic resins, urethane resins, acrylic silicone resins, fluororesins, and composites thereof. . The undercoat material may contain a pigment such as titanium oxide.

As a method for applying the undercoat material, a known method can be employed. For example, spray coating, roller coating, brush coating, and the like are possible. The coating amount of the undercoat material may be set within a range in which the underlying concavo-convex pattern is maintained, and is usually about 0.1 to 0.5 kg / m ² .

In said (2), an uneven | corrugated pattern is formed in the coating-film surface at the time of coating of a coating material or after coating.
In such a method, a concavo-convex pattern can be imparted by the coating film of the coating material. Specifically, various uneven patterns can be formed by performing coating by appropriately setting a coating instrument or viscosity at the time of coating the coating material. In addition, after the coating material is distributed to the base, before the coating film is dried, various uneven patterns can be formed by treating the coating film surface with a design roller, a trowel, a brush, a comb, a spatula, etc. You can also. The coating amount of the covering material is usually about 0.2 to ² kg / m ² , preferably about 0.3 to 1.5 kg / m ² .

  Moreover, in said (2), after coating a coating | covering material on the foundation | substrate, an uneven | corrugated pattern can also be provided by giving embossing etc. This method is particularly useful when a coated body is manufactured in a factory.

  In the coated body of the present invention, a coating film having a contact angle with water of 110 ° or more (preferably 120 ° or more, more preferably 130 ° or more) can be formed. Such water repellency also acts effectively on the contamination prevention effect. In addition, the contact angle said here is a value of the static contact angle measured with a contact angle meter.

  Examples are given below to clarify the features of the present invention.

(Manufacture of coating materials)
According to the composition shown in Tables 1 to 3, each coating material was produced by mixing and stirring each raw material by a conventional method. The following were used as raw materials. In addition, all the granular materials 1-4 are non-spherical.

Resin 1: multilayer structure type synthetic resin emulsion outer layer; acrylic resin (Tg 45 ° C., component: t-butyl methacrylate, n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid; carboxyl group-containing monomer 5 weight %), Silicone resin (component: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane), weight ratio of outer layer acrylic resin to silicone resin 80:20,
Inner layer: acrylic resin (Tg-50 ° C., component: n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate), outer layer / inner layer weight ratio 45:55, solid content 50% by weight

Resin 2: Multi-layer structure type synthetic resin emulsion outer layer; acrylic resin (Tg 45 ° C., component: t-butyl methacrylate, n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid; carboxyl group-containing monomer 5 weight %), Silicone resin (component: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane), weight ratio of outer layer acrylic resin to outer layer silicone resin 80:20,
Inner layer: acrylic resin (Tg-50 ° C., component: n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate), silicone resin (component: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclo) Pentasiloxane), weight ratio of inner layer acrylic resin to inner layer silicone resin 80:20,
Weight ratio of outer layer to inner layer 45:55, solid content 50% by weight

Resin 3: multilayer structure type synthetic resin emulsion outer layer; acrylic resin (Tg 45 ° C., component: t-butyl methacrylate, n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid; carboxyl group-containing monomer 5 weight %), Silicone resin (component: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, γ-methacryloyloxypropyltrimethoxysilane), weight ratio of outer layer acrylic resin to outer layer silicone resin 92: 8,
Inner layer: acrylic resin (Tg-50 ° C., component: n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate), silicone resin (component: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclo) Pentasiloxane, γ-methacryloyloxypropyltrimethoxysilane), inner layer acrylic resin and inner layer silicone resin weight ratio 92: 8,
Weight ratio of outer layer to inner layer 45:55, solid content 50% by weight

Resin 4: Multilayer structure type synthetic resin emulsion Outer layer: Acrylic resin (Tg 45 ° C., component: t-butyl methacrylate, n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid; carboxyl group-containing monomer 5 weight %), Silicone resin (components: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane), weight ratio of outer layer acrylic resin to outer layer silicone resin 55:45,
Inner layer: acrylic resin (Tg-50 ° C., component: n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate), silicone resin (component: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclo) Pentasiloxane), a weight ratio of inner layer acrylic resin to inner layer silicone resin 55:45,
Weight ratio of outer layer to inner layer 45:55, solid content 50% by weight

Resin 5: Synthetic resin emulsion with multilayer structure Outer layer; Acrylic resin (Tg 45 ° C., component: t-butyl methacrylate, n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid; carboxyl group-containing monomer 5 weight %),
Inner layer: silicone resin (component: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane),
Weight ratio of outer layer to inner layer 70:30, solid content 50% by weight

Resin 6: multilayer structure type synthetic resin emulsion outer layer; acrylic resin (Tg 45 ° C., component: t-butyl methacrylate, n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid; carboxyl group-containing monomer 5 weight %),
Inner layer: acrylic resin (Tg-50 ° C., constituent components: n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate),
Weight ratio of outer layer to inner layer 50:50, solid content 50% by weight

Resin 7: Acrylic resin emulsion (Tg 12 ° C., component: t-butyl methacrylate, n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid; solid content 50% by weight)

Resin 8: Cross-linking reaction type acrylic resin emulsion (Tg 20 ° C., component: methyl methacrylate, styrene, 2-ethylhexyl acrylate, diacetone acrylamide, acrylic acid, cross-linking agent; adipic acid dihydrazide, solid content 50% by weight)

・ Crosslinking agent: Epoxy group-containing compound (polyhydroxyalkane polyglycidyl ether)
-Granule 1: Silica powder (average particle size 18 μm, oil absorption 10 ml / 100 g, specific gravity 2.7)
-Granule 2: Silica powder (average particle diameter 4 μm, oil absorption 10 ml / 100 g, specific gravity 2.7)
-Granule 3: Silica powder (average particle diameter 72 μm, oil absorption 10 ml / 100 g, specific gravity 2.7)
-Granules 4: Talc (average particle diameter 12 μm, oil absorption 35 ml / 100 g, specific gravity 2.7)
-Granule 5: Diatomaceous earth (average particle diameter 9 μm, oil absorption 170 ml / 100 g, specific gravity 2.3)
Coloring pigment 1: Titanium oxide (average particle size 0.2 μm, oil absorption 13 ml / 100 g, specific gravity 4.2)
Coloring pigment 2: Fast yellow 10G (average particle size 0.2 μm, oil absorption 40 ml / 100 g, specific gravity 1.6)
・ Water repellent: dimethylsiloxane compound dispersion, solid content 50% by weight)
・ Film-forming auxiliary: 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate ・ Dispersant: polycarboxylic acid-based dispersant (solid content 30% by weight)
・ Thickener: Polyurethane thickener (solid content 30% by weight)
-Antifoaming agent: Silicon-based antifoaming agent (solid content 50% by weight)

(Test Examples 1 to 24)
In Test Examples 1-24, the test shown below was done using the coating materials 1-24 obtained by the said method, respectively. The results are shown in Tables 4-6.

(1) Contact angle measurement An epoxy resin primer (pigment volume concentration 0%, the same shall apply hereinafter) is spray-coated on an aluminum plate (150 × 70 mm) at a coating amount of 0.1 kg / m ² , a temperature of 23 ° C. and a relative humidity. After drying for 8 hours under 50% (hereinafter, standard state), the coating material obtained by the above method was diluted 10% with water and spray-coated at a coating amount of 0.2 kg / m ^2. The test specimen was dried for 14 days. 0.2 cc of deionized water was dropped on the surface of the test specimen, and the contact angle immediately after dropping was measured with a CA-A type contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd.

(2) Paintability test After spray coating an epoxy resin primer at a coating amount of 0.1 kg / m ² on a slate plate (900 × 900 mm) and drying for 8 hours in a standard state, each coating material was treated with 10 parts of water. The surface state was confirmed when spray coating was performed at a coating amount of 0.2 kg / m ² after dilution at 1%. The evaluation criteria were “◯” when no repelling occurred, “△” when slightly repelling, and “X” clearly repelling.

(3) Water resistance test A siding board (150 × 70 mm) having a concavo-convex pattern was spray-coated with an epoxy resin primer at a coating amount of 0.1 kg / m ² and dried in a standard state for 8 hours. 10% diluted with water and spray-coated at a coating amount of 0.2 kg / m ² and cured for 14 days was used as a test specimen. After this test body was immersed in warm water at 50 ° C. for 24 hours, the adhesion was evaluated by a cross-cut tape method according to JIS K 5600-5-6. The evaluation criteria are “」 ”when the defect area is less than 5%,“ ◯ ”when the defect area is 5% or more and less than 15%, and“ △ ”when the defect area is 15% or more and less than 35%. “,” And “x” are those having a defect area of 35% or more.

(4) Wet cooling and heat resistance test After spray coating an epoxy resin primer at a coating amount of 0.1 kg / m ² on a siding board (150 × 70 mm) having a concavo-convex pattern, and drying in a standard state for 8 hours, Each coating material was diluted 10% with water, spray-coated at a coating amount of 0.2 kg / m ² , and cured for 14 days. The specimen was immersed in water at 23 ° C. for 18 hours, immediately cooled in a thermostat kept at −20 ° C. for 3 hours, and then heated in another thermostat kept at 50 ° C. for 3 hours. After this operation was repeated 10 times, it was placed in a standard state for about 1 hour, and the state of the coating film surface was visually observed. Evaluation criteria are based on checking the degree of occurrence of abnormalities (cracking, swelling, and peeling). “◎” indicates that no abnormality occurred, “○” indicates that no abnormality occurred, “△” indicates that a part of the mark was generated, and “X” indicates a case where the abnormality was significantly generated.

(5) Water repellency persistence test An aluminum plate (150 × 70 mm) was spray-coated with an epoxy resin primer at a coating amount of 0.1 kg / m ² and dried in a standard state for 8 hours. A test specimen was prepared by spraying with a coating amount of 0.2 kg / m ² and drying for 14 days in a standard state. 0.2 cc of deionized water was dropped on the surface of the test specimen, and the contact angle immediately after dropping was measured with a CA-A type contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd.
Next, the test specimen was immersed in water at 23 ° C. for 3 hours, dried in a standard state for 1 hour, and then the contact angle was measured in the same manner. In this test, the contact angle after immersion in water was evaluated by confirming how much the contact angle decreased with respect to the initial contact angle. The evaluation criteria are “◯” when the contact angle decrease after water immersion is less than 5 degrees, “△” when 5 degrees or more and less than 10 degrees, and “×” when 10 degrees or more. "

(6) Contamination prevention test (6-1) Contamination prevention test 1
A slate plate (150 × 70 mm) is spray-coated with an epoxy resin primer at a coating amount of 0.1 kg / m ² , dried in a standard state for 8 hours, and then coated with a thin finish coating material of JIS A6909. Spray coating was performed at a rate of ² kg / m ² , and drying was performed for 24 hours in a standard state, so that a base having an uneven pattern (a height difference of 1 to 2 mm) was produced. Each coating material was diluted 10% with water and spray-coated at a coating amount of 0.2 kg / m ² on this base, and cured for 14 days to obtain a test specimen. The test specimen was tilted 15 degrees with respect to the horizontal plane, and 2 cc of commercially available soy sauce was dropped on the coating film surface of the test specimen using a spoid, and after standing for 15 minutes, water was poured on the coating film surface. The state of the coating film surface at this time was confirmed visually. The evaluation criteria were four stages (◎>○>Δ> ×) where “◎” indicates that no stain was observed and “×” indicates that the stain was significantly observed.

(6-2) Contamination prevention test 2
A test specimen was prepared in the same manner as in the anti-staining test 1, the test specimen was tilted by 15 degrees with respect to the horizontal plane, and a spoid was used on the coating film surface of the test specimen. 2 cc of a 01% aqueous solution was dropped, and after standing for 15 minutes, water was allowed to flow over the surface of the coating film. The state of the coating film surface at this time was evaluated according to the same criteria as in the contamination prevention test 1.

(6-3) Contamination prevention test 3
Prepare a test specimen in the same manner as in the above-mentioned pollution prevention test 1, tilt this test specimen by 15 degrees with respect to the horizontal surface, drop 2 cc of commercially available vegetable oil onto the coating surface of the test specimen using a spoid, and leave it for 15 minutes. Thereafter, the remaining vegetable oil was removed with dry gauze, and then the surface of the coating film was wiped with gauze soaked with a neutral detergent. The state of the coating film surface at this time was evaluated according to the same criteria as in the contamination prevention test 1.

(6-4) Contamination prevention test 4
A test specimen was prepared in the same manner as in the contamination prevention test 1, and the black rubber was rubbed against the coating film surface of the test specimen, and then wiped with water. The state of the coating film surface at this time was evaluated according to the same criteria as in the contamination prevention test 1.

(7) Water permeability test A slate plate (400 × 200 mm) was spray-coated with an epoxy resin primer at a coating amount of 0.1 kg / m ² and dried for 8 hours in a standard state. The test specimen was diluted and spray-coated at a coating amount of 0.2 kg / m ² and cured for 14 days. The water permeability of the obtained specimen was measured according to the procedure of JIS A 6909 7.13 “Water permeability test B method”. The evaluation criteria were “◎” when the water permeability was less than 0.2 ml, “◯” when 0.2 to 0.5 ml, “Δ” when 0.5 to less than 1 ml, and “×” when more than 1 ml.

(Test Example 25)
Spray the epoxy resin primer on the slate plate (150 x 70 mm) at a coating amount of 0.1 kg / m ² , and after drying for 8 hours in a standard state, the coating material 6 is diluted by 10% with water and applied. The coating was carried out with a wool roller in an amount of 0.1 kg / m ² . After drying for 2 hours, the coating material 6 is applied undiluted at a coating amount of 0.35 kg / m ² using a porous roller, and immediately applied using a design roller (having reticulated irregularities on the roller surface). An uneven pattern (altitude difference of about 1 mm) was formed on the surface. Then, what was cured for 14 days was made into the test body. About this test body, the pollution prevention test was done by the method similar to the said pollution prevention tests 1-4. The test results are shown in Table 6.

(Test Example 26)
A base (having a height difference of about 1 mm) having a concavo-convex pattern was produced by pasting a commercially available paint base cloth on a gypsum board (150 × 70 mm). The coating material 6 was diluted 10% with water and coated with a wool roller at a coating amount of 0.2 kg / m ² on this base, and then cured for 14 days to give a test specimen. About this test body, the pollution prevention test was done by the method similar to the said pollution prevention tests 1-4. The test results are shown in Table 6.

Claims (3)

It is a painted body having a concavo-convex pattern, at least on its surface,
Synthesis in which emulsion resin contains acrylic resin having (meth) acrylic acid alkyl ester as main monomer component and silicone resin having siloxane compound as main monomer component in a weight ratio of 99: 1 to 30:70. Resin emulsion (A), an average particle diameter of 0.5 to 500 μm, an oil absorption of 60 ml / 100 g or less powder (B) as an essential component, the pigment volume concentration of the powder (B) is 10 to 90% A coated body characterized in that a coating film is formed by a certain covering material. For the groundwork with an uneven pattern,
Synthesis in which emulsion resin contains acrylic resin having (meth) acrylic acid alkyl ester as main monomer component and silicone resin having siloxane compound as main monomer component in a weight ratio of 99: 1 to 30:70. Resin emulsion (A), an average particle diameter of 0.5 to 500 μm, an oil absorption of 60 ml / 100 g or less powder (B) as an essential component, the pigment volume concentration of the powder (B) is 10 to 90% A certain covering material
A method for forming a coated body, wherein the coating is applied so that the uneven pattern is maintained. For the groundwork
Synthesis in which emulsion resin contains acrylic resin having (meth) acrylic acid alkyl ester as main monomer component and silicone resin having siloxane compound as main monomer component in a weight ratio of 99: 1 to 30:70. Resin emulsion (A), an average particle diameter of 0.5 to 500 μm, an oil absorption of 60 ml / 100 g or less powder (B) as an essential component, the pigment volume concentration of the powder (B) is 10 to 90% Apply a certain covering material,
A method for forming a coated body, comprising providing an uneven pattern on a coating film surface of the covering material.