JP6227256B2 - Decorative wall - Google Patents

Description

  The present invention relates to a decorative wall surface in a building or the like.

Conventionally, a decorative film having various patterns is formed on a wall surface of a building, a civil engineering structure, or the like. An example of such a decorative coating is a patterned coating in which colored resin particles of a plurality of colors are mixed.
For example, Patent Document 1 describes that a paint obtained by mixing microcapsules in an aqueous composition having a resin component is applied onto a substrate to obtain a pattern film. Patent Document 2 describes that after applying an undercoat paint on a substrate surface, a pattern is formed by applying a paint containing colored paint particles and a coating film forming component.

  However, if the wall surface having such a pattern coating is exposed outdoors for a long period of time, it may be contaminated by the influence of rainfall, dust, etc., and the aesthetics of the corner may be impaired. In particular, in such a pattern coating, there is a possibility that the initial contrast due to the colored resin particles of a plurality of colors is diminished.

  Moreover, the pattern coating like the above-mentioned patent document has a possibility that followability is deteriorated due to long-term outdoor exposure, and there is a possibility of causing defects such as cracks. Such inconvenience is likely to occur particularly when a wall surface is constituted by a plurality of plate-like wall materials provided and joints between the plate-like wall materials are treated with a sealing material or the like.

Japanese Patent Laying-Open No. 2005-330396 JP 2007-296459 A

  The present invention has been made in view of the above-described problems. On the wall surface provided with a plurality of plate-like wall materials, the present invention imparts aesthetics by a pattern of a plurality of colors, and progress of contamination and follow-up performance. The purpose of this is to suppress the deterioration of the glass and maintain the initial aesthetics over a long period of time.

  As a result of intensive studies to achieve the above object, the present inventor has conceived that a specific treated film (A), a patterned film (B), and a transparent film (C) are provided as decorative films, respectively. The invention has been completed.

That is, the present invention has the following characteristics.
1. A decorative wall surface with a decorative coating on the base,
The base is filled with a sealing material and / or putty material at joints between adjacent plate-like wall materials,
As the decorative coating, a treated coating (A), a patterned coating (B), and a transparent coating (C) are sequentially provided on the base,
The treated film (A) has an elongation of 30 to 500%,
The patterned coating (B) is obtained by fixing colored resin particles (b1) of two or more colors to a transparent coating (b2) having a piperidine compound, and the particle size of the colored resin particles (b1) is 0. .1-20 mm,
The transparent coating (b2) contains a resin component and a piperidine compound, and contains 0.01 to 50 parts by weight of a piperidine compound with respect to 100 parts by weight of the solid content of the resin component.
The decorative coating (C) is a decorative wall surface comprising silica having an average primary particle diameter of 1 to 200 nm and a resin component.
2. The transparent coating (C) contains silica having an average primary particle size of 1 to 200 nm and a resin component, and the solid content weight ratio between the silica and the resin component is 0.5: 1 to 5: 1. Features 1 The decorative wall surface described.

  According to the present invention, on the wall surface provided with a plurality of plate-like wall materials, the appearance of a plurality of colors is imparted, and the progress of contamination and the deterioration of the followability are suppressed, and the initial aesthetics are prolonged. Can be held over.

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

  The decorative wall surface of the present invention is provided with a decorative film on the base, and the base is filled with a sealing material and / or a putty material at joints between adjacent plate-like wall materials. .

  Although it does not specifically limit as a plate-shaped wall material, For example, a cement board, an extrusion molding board, a slate board, a PC board, an ALC board, a fiber reinforced cement board, a metal system siding board, a ceramic siding board, a ceramic board, a calcium silicate A board, a gypsum board, a plastic board, a hard wood piece cement board, a PVC extrusion siding board, a plywood board, a pearlite board, etc. are mentioned. The surface of these plate-like wall materials may be subjected to some surface treatment (for example, a sealer, a surfacer, a filler, etc.).

  In the present invention, the plurality of plate-like wall materials are provided side by side through joint portions. That is, a joint portion is provided between the plate-like wall materials. The width of the joint portion is preferably about 3 to 20 mm (more preferably 5 to 15 mm). This joint is filled with a sealing material and / or a putty material.

  Examples of the sealing material filled in the joints between the plate-like wall materials include, for example, silicone-based sealing materials, modified silicone-based sealing materials, polysulfide-based sealing materials, modified polysulfide-based sealing materials, acrylic urethane-based sealing materials, and polyurethane-based sealing materials. Materials, SBR sealants, butyl rubber sealants, and the like. As putty materials, silicone-based putty materials, modified silicone-based putty materials, polysulfide-based putty materials, modified polysulfide-based putty materials, acrylic urethane-based putty materials, polyurethane-based putty materials, acrylic-based putty materials, SBR-based putty materials, butyl rubber-based materials A putty material etc. are mentioned.

Such a sealing material and putty material may be appropriately selected and used depending on the shape of the end of the plate-like wall material, the width and depth of the joint portion to be formed, etc., and only one of them is used. Or they may be used in combination.
The filling method of the sealing material or the putty material is not particularly limited, and for example, a known method using a gun or a spatula can be employed.
In addition, before filling the sealing material and / or putty material, treatment such as filling with a backup material or primer application may be performed in advance. May be performed.

  In the present invention, a specific treated film (A), a patterned film (B), and a transparent film (C) are provided as decorative films on the surface of the base. Specifically, the treated coating (A) has an elongation of 30 to 500%. The patterned coating (B) is obtained by fixing the colored resin particles (b1) to the transparent coating (b2) having a piperidine compound. The transparent coating (C) contains silica having an average primary particle diameter of 1 to 200 nm and a resin component.

In the present invention, by laminating such a treated coating (A), pattern coating (B), and transparent coating (C), it is possible to impart aesthetics by a pattern of a plurality of colors, and to promote the progress of contamination of the cosmetic coating. It is possible to suppress the deterioration of the sex and maintain the initial aesthetics for a long time. In particular, in the present invention, the contrast of a pattern of a plurality of colors due to colored resin particles can be maintained for a long time.
In the present invention, the adhesion between the pattern coating (B) and the transparent coating (C) is maintained for a long time by the action of the piperidine compound in the pattern coating (B). Furthermore, the piperidine compound in the pattern coating (B) can exhibit its performance for a long time due to the protective effect of the transparent coating (C). This piperidine compound also contributes to maintaining followability. In addition, the pollutant easily stores heat, and the heat may promote deterioration of the decorative film. However, in the present invention, adverse effects due to such a pollutant can also be suppressed. In the present invention, it is presumed that the effect of maintaining aesthetics is sufficiently exhibited by these synergistic actions.

[Treatment film (A)]
The treated film (A) has a performance of relaxing the displacement while following the displacement of the base. In the present invention, cracks and peeling of the decorative coating can be sufficiently suppressed by the action of the treatment coating.

  The elongation percentage of the treated film (A) is usually 30 to 500%, preferably 50 to 300%. When the elongation rate is within such a range, followability to the base is exhibited and cracking of the decorative film is also prevented. If the elongation percentage is smaller than 30%, the followability to the base cannot be secured, and cracks may occur in the treated coating (A). If the elongation is greater than 500%, the pattern coating (B) is likely to crack.

  The elongation of the treated coating (A) is a value (elongation at 20 ° C.) measured by the method of “Elongation test at 20 ° C.” of JIS A6909 “7.29 Elongation test”. However, a test piece having a dry film thickness of 0.3 mm is used.

In the treated film (A), various resin components can be used as long as the above physical properties are satisfied. Usable resins include, for example, acrylic resins, urethane resins, vinyl acetate resins, vinyl chloride resins, epoxy resins, urethane resins, silicone resins, fluororesins, acrylic vinyl acetate resins, acrylic urethane resins, acrylic silicone resins, etc. One or more of these can be used. Among these, acrylic resin, acrylic silicon resin, and the like are preferable.
The glass transition temperature of such a resin component is preferably −50 ° C. to 30 ° C., more preferably −40 ° C. to 25 ° C. The glass transition temperature is a value determined by the FOX equation.

  The treated film (A) can be formed by applying and drying a coating material containing the resin component (hereinafter also referred to as “coating material A”). The covering material A may contain various components other than the above components as long as the effects of the present invention are not significantly impaired. Examples of such components include coloring pigments, extender pigments, matting agents, thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreezing agents, pH adjusting agents, preservatives, and antifungal agents. Agents, anti-algae agents, antibacterial agents, dispersants, antifoaming agents, adsorbents, fibers, cross-linking agents, ultraviolet absorbers, antioxidants, catalysts and the like.

The elongation percentage of the treated coating (A) can be appropriately set depending on, for example, the type of resin component, glass transition temperature, pigment ratio when pigments are mixed, and the like.
The pigment ratio of the treated coating (A) is preferably 0 to 500 parts by weight, more preferably 10 to 300 parts by weight, and further preferably 20 to 200 parts by weight with respect to 100 parts by weight of the solid content of the resin component.

When the coating material A is applied to the ground, a known coating instrument such as a brush, a roller, or a spray can be used. The covering material A may be applied approximately 2 to 10 days after the joint material is filled with a sealing material or putty material. The coating amount of the coating material A is preferably about 10 to 300 g / m ^{2 in} terms of solid content.

[Pattern film (B)]
As the colored resin particles (b1) in the pattern coating (B), those containing a resin component and a colored pigment can be used. The particle diameter of the colored resin particles (b1) is not particularly limited, but is preferably 0.1 to 20 mm, more preferably 0.5 to 10 mm.

  Examples of the resin component in the colored resin particles (b1) include acrylic resin, urethane resin, vinyl acetate resin, silicon resin, fluororesin, acrylic vinyl acetate resin, acrylic urethane resin, and acrylic silicon resin. Species or two or more can be used. Such a resin component is preferably a water-soluble resin and / or a water-dispersible resin.

Examples of color pigments include titanium oxide, zinc oxide, alumina, carbon black, ferric oxide (valve), yellow iron oxide, iron oxide, ultramarine, cobalt green, and other inorganic color pigments, azo-based, naphthol-based, Examples include pyrazolone-based, anthraquinone-based, perylene-based, quinacridone-based, disazo-based, isoindolinone-based, benzimidazole-based, phthalocyanine-based, quinophthalone-based organic color pigments, pearl pigments, aluminum pigments, fluorescent pigments, and the like. The colored resin particles (b1) can be prepared in a desired color tone by combining one or more of such colored pigments. In the colored resin particles (b1), an extender pigment can be used in addition to such a colored pigment.
As the colored resin particles (b1), those containing 0.01 to 200 parts by weight of color pigment are preferable and more preferably those containing 0.1 to 100 parts by weight with respect to 100 parts by weight of the solid content of the resin component.

  The colored resin particles (b1) described above are fixed to the transparent coating (b2). The transparent coating (b2) preferably contains a resin component in order to fix the colored resin particles (b1) described above. Examples of such resin components include acrylic resins, urethane resins, vinyl acetate resins, urethane resins, silicone resins, fluororesins, acrylic vinyl acetate resins, acrylic urethane resins, acrylic silicone resins, and the like. Or 2 or more types can be used. Such a resin component is preferably a water-soluble resin and / or a water-dispersible resin.

As the piperidine compound in the transparent film (b2), a compound having a piperidyl group can be used. As a form of this piperidine compound,
A) Form existing as a component different from the resin component, and / or
B) A chemically bonded form in the resin component
Is mentioned. In the present invention, the above a) and a) may be combined.

In the form a), a non-polymerizable piperidine compound can be used. Specifically, examples of such a compound include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-piperidyl). Sebacate, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), tetrakis (2 , 2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2 , 3,4-Butanetetracarboxylate, methyl (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, N, N ′, N ″, N ″ ′-tetrakis- (4,6-bis (Butyl- (N-Me -2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, N, N'-bis- (2, 2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine, N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, 4-hydroxy-2,2,6 , 6-Tetramethyl-1-piperidineethanol, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidyl) ester, 4-benzoyloxy-2,2,6, 6-tetramethylpiperidine, 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethyl A Emissions) -1,3,5-triazine, and derivatives thereof. These may be used alone or in combination of two or more.

  In the form of the above a), it is preferable to contain 0.01 to 50 parts by weight of the piperidine compound, more preferably 0.1 to 30 parts by weight, and still more preferably 0.5 to 100 parts by weight of the solid content of the resin component. ~ 20 parts by weight. Such a ratio is preferable in terms of manifesting the effects of the present invention.

  In the form (a), since the piperidine compound is chemically bonded to the resin component, a polymerizable piperidine compound can be used. As such a compound, a compound having a piperidyl group and a polymerizable unsaturated double bond can be used. For example, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meta ) Acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-1,2, 2,6,6-pentamethylpiperidine, 4-cyano-4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1-methylcarbamoyloxy-2, 2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpipe Gin, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonyloxy-2,2,6,6-tetramethylpiperidine and the like. These can be used alone or in combination of two or more.

  Such a polymerizable piperidine compound can be chemically bonded to the resin component by copolymerizing with other monomers at the time of production (polymerization) of the resin component by a known method. The ratio of the piperidine compound in the resin component is preferably 0.01 to 20% by weight, more preferably 0.1 to 15% by weight. Such a ratio is preferable in terms of manifesting the effects of the present invention.

  The pattern coating (B) may be in any form as long as the colored resin particles (b1) are dispersed in the transparent coating (b2), but the colored resin particles (b1) having two or more colors (more preferably 3 to 8 colors) are included. A form scattered in the transparent coating (b2) is preferred. The solid content weight ratio of the colored resin particles (b1) to the transparent coating (b2) in the pattern coating (B) is preferably 0.1: 1 to 5: 1, more preferably 0.3: 1 to 3: 1. It is. If it is such a form, aesthetics can be improved further.

The pattern coating (B) includes a resin component, and a coating material (hereinafter also referred to as “coating material B”) in which liquid or gel colored resin particles are dispersed in a dispersion medium having a piperidine compound is applied and dried. Can be formed. In such a coating material B, the components in the dispersion medium form a transparent coating (b2), and the liquid or gel colored resin particles are dried and fixed to the transparent coating (b2). In the present invention, by using the coating material B, the pattern film (B) can be efficiently formed by one coating. The coating of the coating material B may be performed using a known coating instrument such as a brush, a roller, or a spray. The coating amount of the coating material B is preferably about ²⁰ to 500 g / m ^{2 in} terms of solid content.

  This coating material B may contain other components in the dispersion medium and / or the colored resin particles as long as the effect of the present invention is not significantly impaired. Examples of such components include matting agents, thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreezing agents, pH adjusting agents, antiseptics, antifungal agents, and antialgal agents. Antibacterial agents, dispersants, antifoaming agents, adsorbents, fibers, crosslinking agents, ultraviolet absorbers, antioxidants, catalysts and the like can be mentioned. The colored resin particles may contain a piperidine compound.

In the patterned coating (B), it is desirable that the colored resin particles (b1) have a flat shape. In such an embodiment, a large pattern can be formed while the pattern coating (B) is relatively thin and lightweight. In order to obtain a patterned coating (B) having flat colored resin particles, for example,
A method of coating the coating material B in which flat colored resin particles are dispersed in advance.
-A method of flattening colored resin particles by the pressure during coating.
-A method of making colored resin particles flat by applying pressure after coating.
Or the like.

  In addition, the flat shape said here means the state where the ratio of the minor axis to the thickness is larger than 2. The short diameter and long diameter of the flat colored resin particles are not particularly limited, but may be preferably about 0.1 to 20 mm (more preferably 0.5 to 10 mm). In the present invention, the range of design properties can be expanded by variously combining flat colored resin particles having different particle diameters.

[Transparent film (C)]
The transparent film (C) in the present invention is provided on the outermost surface of the decorative film. This transparent film (C) contains silica having an average primary particle diameter of 1 to 200 nm and a resin component.

Among these, silica exhibits a superior anti-contamination effect due to the high hardness of the particles themselves and the fact that they have many silanol groups on the surface of the particles.
The average primary particle diameter of silica is usually 1 to 200 nm, preferably 3 to 100 nm. Within this range, a plurality of silicas having different average primary particle sizes can be used in combination. When the average primary particle diameter of silica is larger than 200 nm, the specific surface area becomes small, and silanol groups are also reduced, so that the antifouling property becomes insufficient. When the average primary particle diameter is smaller than 1 nm, the silica itself becomes unstable, so it is not practical. In addition, the average primary particle diameter said here is a value measured by the light-scattering method.

The silica of the transparent coating (C) is preferably derived from a silica sol, and further derived from a water-dispersible silica sol having a pH of 5.0 or more and less than 8.5 (preferably 6.0 or more and 8.0 or less). Is more preferred.
Such a neutral type water-dispersible silica sol can be produced using a silicate compound as a raw material. Examples of the silicate compound include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraisobutoxysilane, tetra sec-butoxysilane, tetra t-butoxysilane, tetra Examples thereof include phenoxysilane and the condensates thereof. In addition, alkoxysilane compounds other than the above silicate compounds, alcohols, glycols, glycol ethers, fluorine alcohols, silane coupling agents, polyoxyalkylene group-containing compounds, and the like can also be used.

  Various resins can be used as the resin component in the transparent coating (C). Specifically, for example, acrylic resin, urethane resin, vinyl acetate resin, silicon resin, fluororesin, acrylic vinyl acetate resin, acrylic urethane resin, acrylic silicon resin, and the like, one or more of these are used. it can. Such a resin component is preferably a water-soluble resin and / or a water-dispersible resin.

  The solid content weight ratio (silica: resin component) of silica and resin component in the transparent coating (C) is preferably 0.5: 1 to 5: 1, more preferably 0.8: 1 to 4: 1, Preferably it is 1: 1-3: 1. If it is such ratio, sufficient effect will be acquired in the pollution prevention effect and adhesiveness with a lower layer film, and the effect of the present invention will be exhibited stably.

  The transparent film (C) can be formed by applying and drying the coating material C containing the above components. The covering material C may contain various components other than the above components as long as the effects of the present invention are not significantly impaired. Such components include, for example, thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreeze agents, pH adjusters, antiseptics, antifungal agents, antialgae agents, antibacterial agents, dispersions Agents, antifoaming agents, crosslinking agents, ultraviolet absorbers, antioxidants and the like. However, it is desirable to avoid the use of a photocatalytic substance because it may cause a decrease in adhesiveness over time and discoloration of the pattern film.

The covering material C may be applied to the entire surface of the pattern coating (B). As a coating instrument, well-known things, such as a brush, a roller, and a spray, can be used, for example. Coating with the amount of the coating material C in forming the transparent film (C) is a solid basis, and preferably from 0.1 to 50 g / ^{m 2,} more preferably 0.5 to 20 g / ^{m 2.}

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

  As the covering material A, the following materials were prepared.

○ Coating material A1
20 parts by weight of titanium oxide, film-forming aid for 200 parts by weight of acrylic silicon resin 1 (water-dispersible resin obtained by emulsion polymerization of acrylic monomer and dimethylsiloxane, glass transition temperature 0 ° C., solid content 50% by weight) 4 parts by weight of the agent, 2 parts by weight of the viscosity modifier, 1 part by weight of the antifoaming agent, and 20 parts by weight of water were uniformly mixed by a conventional method. The elongation percentage of the covering material A1 was 250%.

○ Coating material A2
20 parts by weight of titanium oxide, 80 parts by weight of heavy calcium carbonate, 4 parts by weight of a film-forming aid, 3 parts by weight of a viscosity modifier, 1 part by weight of an antifoaming agent with respect to 200 parts by weight of acrylic silicon resin 1 (same as above) Then, 50 parts by weight of water was uniformly mixed by a conventional method. The elongation percentage of the covering material A2 was 170%.

○ Coating material A3
20 parts by weight of titanium oxide, heavy carbonic acid with respect to 200 parts by weight of acrylic silicon resin 2 (water-dispersible resin obtained by emulsion polymerization of acrylic monomer and dimethylsiloxane, glass transition temperature 12 ° C., solid content 50% by weight) 80 parts by weight of calcium, 4 parts by weight of a film-forming aid, 3 parts by weight of a viscosity modifier, 1 part by weight of an antifoaming agent and 50 parts by weight of water were uniformly mixed by a conventional method. The elongation percentage of the covering material A3 was 90%.

○ Coating material A4
20 parts by weight of titanium oxide and heavy carbonic acid with respect to 200 parts by weight of epoxy-modified acrylic resin (water-dispersible resin obtained by emulsion polymerization of acrylic monomer and epoxy compound, glass transition temperature 35 ° C., solid content 50% by weight) 80 parts by weight of calcium, 4 parts by weight of a film-forming aid, 3 parts by weight of a viscosity modifier, 1 part by weight of an antifoaming agent and 50 parts by weight of water were uniformly mixed by a conventional method. The elongation percentage of the covering material A4 was 20%.

  As the coating material B, the following materials were prepared.

○ Coating material B1
The following three kinds of colored resin particles are an aqueous dispersion medium 1 (acrylic resin emulsion, piperidine compound (bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate)) and aqueous dispersion mainly composed of water. A coating material B1 dispersed in a medium containing 3 parts by weight of a piperidine compound per 100 parts by weight of the solid content of the resin component was produced. This aqueous dispersion medium 1 forms a transparent film, and the solid content weight ratio between the colored resin particles and the aqueous dispersion medium 1 is 1.5: 1.
The colored resin particles are flat black particles (acrylic resin emulsion, black iron oxide, yellow iron oxide, petal, titanium oxide, gel particles mainly composed of water. Resin component: colored pigment = 100: 15 (solid content Weight ratio), particle diameter of about 2 mm) and flat dark gray particles (gel particles mainly composed of acrylic resin emulsion, black iron oxide, titanium oxide and water. Resin component: Color pigment = 100: 21 (solid content) (Weight ratio), particle diameter of about 1 mm) and flat light gray particles (gel particles mainly composed of acrylic resin emulsion, black iron oxide, titanium oxide and water. Resin component: colored pigment = 100: 32 (solid content) Weight ratio), particle diameter of about 1 mm), and flat black particles: flat dark gray particles: flat light gray particles = 1: 1: 1 (solid content weight ratio).

○ Coating material B2
The above three kinds of colored resin particles (similar to the coating material B1) are dispersed in an aqueous dispersion medium 2 (acrylic resin emulsion, piperidine compound (bis (2,2,6,6-tetramethyl-1- (octyloxy) decanedioate)). -4-piperidinyl) ester compound), an aqueous dispersion medium containing water as a main component, and containing 3 parts by weight of a piperidine compound with respect to 100 parts by weight of the solid content of the resin component. The aqueous dispersion medium 2 forms a transparent film, and the solid content weight ratio between the colored resin particles and the aqueous dispersion medium 2 is 1.5: 1.

○ Coating material B3
The above three kinds of colored resin particles (similar to the coating material B1) are dispersed in an aqueous dispersion medium 3 (acrylic resin emulsion, piperidine compound (bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate)), water A coating material B3 in which 8 parts by weight of a piperidine compound is contained per 100 parts by weight of the solid content of the resin component is produced. This aqueous dispersion medium 3 forms a transparent film, and the solid content weight ratio between the colored resin particles and the aqueous dispersion medium 3 is 1.5: 1.

○ Coating material B4
The above three kinds of colored resin particles (similar to the coating material B1) are dispersed in an aqueous dispersion medium 4 (acrylic resin emulsion, piperidine compound (bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate)), water A coating material B4 in which 13 parts by weight of a piperidine compound is contained per 100 parts by weight of the solid content of the resin component is manufactured. The aqueous dispersion medium 4 forms a transparent film, and the solid content weight ratio between the colored resin particles and the aqueous dispersion medium 4 is 1.5: 1.

○ Coating material B5
The above three kinds of colored resin particles (similar to the coating material B1) are dispersed in an aqueous dispersion medium 5 (acrylic resin emulsion, piperidine compound (bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate)), water A coating material B5 in which 18 parts by weight of a piperidine compound is contained per 100 parts by weight of the solid content of the resin component is produced. The aqueous dispersion medium 5 forms a transparent film, and the solid content weight ratio between the colored resin particles and the aqueous dispersion medium 5 is 1.5: 1.

○ Coating material B6
A coating material B6 in which the above three kinds of colored resin particles (similar to the coating material B1) are dispersed in an aqueous dispersion medium 6 (acrylic resin emulsion, aqueous dispersion medium containing water as a main component and not containing a piperidine compound) is produced. did. The aqueous dispersion medium 6 forms a transparent film, and the solid content weight ratio between the colored resin particles and the aqueous dispersion medium 6 is 1.5: 1.

  As the covering material C, the following materials were prepared.

○ Clad material C1
Silica 1 (water-dispersible silica sol, pH 7.6, average primary particle size 27 nm): Acrylic silicone resin (methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-γ-methacryloyloxypropyltrimethoxysilane copolymer resin, glass transition (Temperature 18 ° C.) = 1.5: 1 (solid content weight ratio) aqueous dispersion.

○ Clad material C2
Silica 2 (water-dispersible silica sol, pH 7.5, average primary particle size 10 nm): acrylic silicon resin (methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-γ-methacryloyloxypropyltrimethoxysilane copolymer resin, glass transition (Temperature 18 ° C.) = 1.5: 1 (solid content weight ratio) aqueous dispersion.

○ Clad material C3
Silica 3 (water-dispersible silica sol, pH 7.8, average primary particle size 30 nm): acrylic silicon resin (methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-γ-methacryloyloxypropyltrimethoxysilane copolymer resin, glass transition (Temperature 18 ° C.) = 1.5: 1 (solid content weight ratio) aqueous dispersion.

○ Clad material C4
Silica 1 (water-dispersible silica sol, pH 7.6, average primary particle size 27 nm): Acrylic silicone resin (methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-γ-methacryloyloxypropyltrimethoxysilane copolymer resin, glass transition A temperature of 18 ° C.) = 0.7: 1 (solid weight ratio).

○ Clad material C5
Silica 1 (water-dispersible silica sol, pH 7.6, average primary particle size 27 nm): Acrylic silicone resin (methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-γ-methacryloyloxypropyltrimethoxysilane copolymer resin, glass transition A temperature of 18 ° C.) = 3.0: 1 (solid weight ratio) in water dispersion.

○ Clad material C6
An aqueous dispersion of acrylic silicon resin (methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-γ-methacryloyloxypropyltrimethoxysilane copolymer resin, glass transition temperature 18 ° C.).

(Test 1)
The coating material A is spray-coated on the slate plate at a coating amount of 80 g / m ² (solid content), and after curing for 6 hours, the coating material B is spray-coated at a coating amount of 150 g / m ² (solid content). A pattern coating was formed. Then, after curing for 1 day, the coating material C was spray-coated at a coating amount of 3 g / m ² (solid content) and cured for 7 days. All painting and curing were performed under standard conditions (temperature 23 ° C., relative humidity 50%).

The test body obtained by the above method was immersed in a contaminant suspension (concentration 1% by weight) for 2 hours, pulled up and allowed to stand for 24 hours in a standard state, and then washed and dried. The contamination state at this time was evaluated visually.
Next, after exposing the test body for 1500 hours with an accelerated weathering tester (“Metal Weather Meter”, manufactured by Daipura Wintes Co., Ltd.), the contamination state by the pollutants was evaluated by the same method as described above.
The evaluation of the contamination state is “A” when the adherence of the contaminant is not recognized, “B” when the adherence of the contaminant is slightly recognized, and “C” when the adherence of the contaminant is recognized. This was performed in three stages (A>B> C).

(Test 2)
Two plate-like wall materials (ceramic siding boats) were provided side by side, and a joint material (width 10 mm) between boards filled with a modified silicone sealing material was used as a test base material.
The coating material A is spray-coated on the entire surface of the test substrate at an application amount of 80 g / m ² (solid content), and after curing for 6 hours, the coating material B is applied at an application amount of 150 g / m ² (solid content). A pattern coating was formed by spray painting. Then, after curing for 1 day, the coating material C was spray-coated at a coating amount of 3 g / m ² (solid content) and cured for 7 days. All painting and curing were performed under standard conditions.

About the test body obtained by the said method, the surface state when it displaced 30% in a horizontal direction with a tension tester in a standard state was observed, and followability was evaluated.
Next, after leaving the test body for 1000 hours in a 70 ° C. incubator, the followability was evaluated by the same method as described above.
The followability was evaluated in three stages (A>B> C) where “A” indicates that no crack was observed and “C” indicates that the crack occurred.

(Test results)
Table 1 shows the coating materials used in the above test and the test results. In Examples 1 to 11, the evaluation of the contamination state was good both before and after promotion of Test 1, and good results were obtained in Test 2 as well.

Claims (2)

A decorative wall surface with a decorative coating on the base,
The base is filled with a sealing material and / or putty material at joints between adjacent plate-like wall materials,
As the decorative coating, a treated coating (A), a patterned coating (B), and a transparent coating (C) are sequentially provided on the base,
The treated film (A) has an elongation of 30 to 500%,
The patterned coating (B) is obtained by fixing colored resin particles (b1) of two or more colors to a transparent coating (b2) having a piperidine compound, and the particle size of the colored resin particles (b1) is 0. .1-20 mm,
The transparent coating (b2) contains a resin component and a piperidine compound, and contains 0.01 to 50 parts by weight of a piperidine compound with respect to 100 parts by weight of the solid content of the resin component.
The decorative coating (C) is a decorative wall surface comprising silica having an average primary particle diameter of 1 to 200 nm and a resin component. The transparent coating (C) contains silica having an average primary particle size of 1 to 200 nm and a resin component, and the solid content weight ratio between the silica and the resin component is 0.5: 1 to 5: 1. The decorative wall surface according to claim 1, wherein