JP2013199826A - Decorative wall surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart a fine appearance with a concave-convex pattern, suppress progress of contamination and deterioration of followability, and hold the initial fine appearance for a long period of time in a decorative wall surface in which a plurality of plate-like wall materials are juxtaposed.SOLUTION: A treatment film(A), a pattern film(B), and a transparent film(C) are provided in this order on a substrate in which joint parts between adjacent plate-like wall materials are filled with a sealant and/or a putty material. The treatment film(A) has an elongation percentage of 30-500%. The pattern film(B) has an irregular pattern on its surface and contains a resin component, a particulate matter, and a piperidine compound, and a ratio of the particulate matter to 100 pts.wt. solid of the resin component is 100 to 4000 pts.wt. The transparent film(C) contains silica of an average primary particle diameter 1-200 nm and a resin component.

Description

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

Conventionally, a decorative film having a three-dimensional uneven pattern is formed on a wall surface of a building or the like. Such a concavo-convex pattern can be expressed by appropriately selecting the type of coating material to be used, the equipment at the time of painting, and the like.
For example, Patent Document 1 describes that an uneven pattern is formed on a painted surface using a thick film coating material mainly composed of a binder and a filler. Patent Document 2 describes that a pattern surface is formed by spraying sand on a dotted main material paint layer formed by applying a main material paint in a dotted pattern. Patent Document 3 describes that after applying a finish coating material, an uneven pattern is formed using a pattern pressing tool.

  However, if the wall surface having such a decorative film is exposed to the outdoors for a long time, it may be contaminated by the influence of rainfall, dust, etc., and the aesthetics of the corner may be impaired. In particular, the concave and convex portions tend to be easily contaminated.

  In addition, a decorative coating such as the above-mentioned patent document has a possibility that followability is lowered due to long-term outdoor exposure, and a defect such as cracking may occur. 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.

JP-A-3-21671 Japanese Patent Laid-Open No. 7-60933 Japanese Patent Application Laid-Open No. 8-3333861

  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 due to the uneven pattern, and the progress of contamination and the follow-up performance are lowered. It is intended to suppress 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 pattern coating (B) has a concavo-convex pattern on the surface thereof, includes a resin component, a granular material, and a piperidine compound, and the ratio of the granular material to 100 parts by weight of the solid content of the resin component is 100 to 4000 parts by weight. And
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. 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) has a concavo-convex pattern on the surface thereof, and includes a resin component and a granular material to which a piperidine compound is bonded, and the ratio of the granular material to 100 parts by weight of the solid content of the resin component is 100 to 4000. Parts by weight,
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.
3. 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 pattern coating (B) has a concavo-convex pattern on the surface thereof, and includes a resin component, a granular material, and a piperidine compound to which a piperidine compound is bonded. 100 to 4000 parts by weight,
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.
4). 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 ~ 3. The decorative wall surface according to any one of the above.

  According to the present invention, on the wall surface provided with a plurality of plate-like wall materials, the aesthetic appearance due to the uneven pattern is imparted, the progress of contamination and the decrease in follow-up performance are suppressed, and the initial aesthetic appearance is maintained for a long time. can do.

  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 pattern coating (B) has a concavo-convex pattern on its surface, and has a resin component, a granular material, and 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 due to the uneven pattern, and to promote the contamination of the cosmetic coating and follow-up performance. The deterioration can be suppressed and the initial aesthetics can be maintained for a long time.
In particular, 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, silicone resins, fluorine resins, acrylic vinyl acetate resins, acrylic urethane resins, acrylic silicon resins, etc. 1 type (s) or 2 or more types 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. In addition, a glass transition temperature is a value calculated | required from the calculation formula of FOX.

  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, the glass transition temperature, and the pigment ratio when pigments are mixed.
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)]
Examples of the concavo-convex pattern of the pattern coating (B) include a sand wall shape, a yuzu skin shape, a ripple shape, a stucco shape, a concavo-convex shape, a lunar surface shape, a comb-drawing shape, and an insect worm shape. What is necessary is just to set suitably the level difference of such an uneven | corrugated pattern in the range of about 0.2-5 mm in general.

  The resin component in the pattern coating (B) acts as a binder for the pattern coating (B). Examples of such a resin component include acrylic resin, urethane resin, vinyl acetate resin, silicon resin, fluorine resin, acrylic vinyl acetate resin, acrylic urethane resin, acrylic silicon resin, and the like. The above can be used. Such a resin component is preferably a water-soluble resin and / or a water-dispersible resin.

  Examples of the granular material in the pattern coating (B) include heavy calcium carbonate, precipitated calcium carbonate, kaolin, talc, clay, porcelain clay, China clay, barium sulfate, barium carbonate, chlorite, quartz sand, quartzite, diatomaceous earth, Titanium oxide, zinc oxide, aluminum oxide, iron oxide, etc. are mentioned, These 1 type (s) or 2 or more types can be used. The average particle diameter of the granular material is preferably 0.1 μm to 5 mm, more preferably 0.2 μm to 3 mm.

  The ratio of the powder is 100 to 4000 parts by weight, preferably 150 to 2000 parts by weight, and more preferably 200 to 1000 parts by weight with respect to 100 parts by weight of the solid content of the resin component. If the ratio of the powder particles is within such a range, a concavo-convex pattern is likely to be formed, which is also preferable in terms of various film properties.

As the piperidine compound in the pattern coating (B), 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, it is particularly preferable to combine the above a) and b).

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 a), it is preferable to contain 0.01 to 20 parts by weight of the piperidine compound, more preferably 0.1 to 15 parts by weight, and still more preferably 0.5 to 100 parts by weight of the solid content of the resin component. -10 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) can be formed by applying and drying the coating material B containing the above components. This coating material B 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 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.

What is necessary is just to select the coating method suitably so that a desired uneven | corrugated pattern may be formed when apply | coating the said coating | covering material B on a base material. For example, a spray, a roller, a brush, a trowel, or the like can be used as the coating instrument. Of course, a plurality of these coating instruments may be used in combination. For example, after spray coating, an uneven pattern can be formed by various design rollers.
The coating amount of the coating material B is preferably about 0.5 to 8 kg / m ^{2 in} terms of solid content.

[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
Acrylic resin 1 (water-dispersible resin obtained by emulsion polymerization of acrylic monomer and polymerizable piperidine compound, polymerizable piperidine compound: 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine (0 in resin component) 0.5 wt.), Glass transition temperature 5 ° C., solid content 50 wt.%) With respect to 200 parts by weight, 240 parts by weight of calcium carbonate, 20 parts by weight of titanium oxide, 10 parts by weight of film-forming aid, 3 parts by weight of viscosity modifier Then, 2 parts by weight of an antifoaming agent and 80 parts by weight of water were uniformly mixed by a conventional method.

○ Coating material B2
Acrylic resin 2 (water-dispersible resin obtained by emulsion polymerization of acrylic monomer and polymerizable piperidine compound, polymerizable piperidine compound: 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine (resin component 0.5 weight%), glass transition temperature 5 ° C., solid content 50 weight%) 200 parts by weight of calcium carbonate 240 parts by weight, titanium oxide 20 parts by weight, film-forming aid 10 parts by weight, viscosity modifier 3 Part by weight, 2 parts by weight of antifoaming agent, and 80 parts by weight of water were uniformly mixed by a conventional method.

○ Coating material B3
240 parts by weight of calcium carbonate, 20 parts by weight of titanium oxide, piperidine compound (bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate) 2 with respect to 200 parts by weight of acrylic resin 1 (same as above) Part by weight, 10 parts by weight of a film-forming aid, 3 parts by weight of a viscosity modifier, 2 parts by weight of an antifoaming agent, and 80 parts by weight of water were uniformly mixed by a conventional method.

○ Coating material B4
200 parts by weight of acrylic resin 1 (same as above), 240 parts by weight of calcium carbonate, 20 parts by weight of titanium oxide, piperidine compound (bis (2,2,6,6-tetramethyl-1- (octyloxy) decanedioate) ) -4-piperidinyl) ester compound) 2 parts by weight, 10 parts by weight of a film-forming aid, 3 parts by weight of a viscosity modifier, 2 parts by weight of an antifoaming agent, and 80 parts by weight of water were uniformly mixed by a conventional method.

○ Coating material B5
Acrylic resin 1 (same as above), 200 parts by weight of calcium carbonate 240 parts by weight, titanium oxide 20 parts by weight, piperidine compound (bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate) 1 Part by weight, 10 parts by weight of a film-forming aid, 3 parts by weight of a viscosity modifier, 2 parts by weight of an antifoaming agent, and 80 parts by weight of water were uniformly mixed by a conventional method.

○ Coating material B6
240 parts by weight of calcium carbonate, 20 parts by weight of titanium oxide, piperidine compound (bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate) 4 with respect to 200 parts by weight of acrylic resin 1 (same as above) Part by weight, 10 parts by weight of a film-forming aid, 3 parts by weight of a viscosity modifier, 2 parts by weight of an antifoaming agent, and 80 parts by weight of water were uniformly mixed by a conventional method.

○ Coating material B7
240 parts by weight of calcium carbonate, 20 parts by weight of titanium oxide, piperidine compound (bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate) 8 with respect to 200 parts by weight of acrylic resin 1 (same as above) Part by weight, 10 parts by weight of a film-forming aid, 3 parts by weight of a viscosity modifier, 2 parts by weight of an antifoaming agent, and 80 parts by weight of water were uniformly mixed by a conventional method.

○ Coating material B8
Acrylic resin 3 (water-dispersible resin obtained by emulsion polymerization of acrylic monomer and polymerizable piperidine compound, polymerizable piperidine compound: 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine (2 in resin component) 0.0 wt.%), Glass transition temperature 5 ° C., solid content 50 wt.%) 200 parts by weight, calcium carbonate 240 parts by weight, titanium oxide 20 parts by weight, piperidine compound (bis (1,2,2,6,6) -Pentamethyl-4-piperidyl) sebacate) 2 parts by weight, 10 parts by weight of a film-forming aid, 3 parts by weight of a viscosity modifier, 2 parts by weight of an antifoaming agent, and 80 parts by weight of water were uniformly mixed by a conventional method.

○ Coating material B9
Acrylic resin 4 (water-dispersible resin obtained by emulsion polymerization of acrylic monomer and polymerizable piperidine compound, polymerizable piperidine compound: 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine (4 in resin component) 0.0 wt.%), Glass transition temperature 5 ° C., solid content 50 wt.%) 200 parts by weight, calcium carbonate 240 parts by weight, titanium oxide 20 parts by weight, piperidine compound (bis (1,2,2,6,6) -Pentamethyl-4-piperidyl) sebacate) 2 parts by weight, 10 parts by weight of a film-forming aid, 3 parts by weight of a viscosity modifier, 2 parts by weight of an antifoaming agent, and 80 parts by weight of water were uniformly mixed by a conventional method.

○ Coating material B10
Acrylic resin 1 (same as above) with respect to 200 parts by weight 550 parts by weight of garnet, 240 parts by weight of calcium carbonate, 20 parts by weight of titanium oxide, piperidine compound (bis (1,2,2,6,6-pentamethyl-4) -Piperidyl) Sebacate) 2 parts by weight, 10 parts by weight of a film-forming aid, 3 parts by weight of a viscosity modifier, 2 parts by weight of an antifoaming agent, and 80 parts by weight of water were uniformly mixed by a conventional method.

○ Coating material B11
240 parts by weight of calcium carbonate with respect to 200 parts by weight of acrylic resin 5 (water-dispersible resin obtained by emulsion polymerization of acrylic monomer (not including polymerizable piperidine compound), glass transition temperature 5 ° C., solid content 50% by weight) Parts, titanium oxide 20 parts by weight, piperidine compound (bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate) 2 parts by weight, film-forming aid 10 parts by weight, viscosity modifier 3 parts by weight, 2 parts by weight of an antifoaming agent and 80 parts by weight of water were uniformly mixed by a conventional method.

○ Coating material B12
240 parts by weight of calcium carbonate, 20 parts by weight of titanium oxide, 10 parts by weight of a film-forming aid, and viscosity modifier for 200 parts by weight of acrylic resin 5 (same as above), glass transition temperature 5 ° C., solid content 50% by weight) 3 parts by weight, 2 parts by weight of an antifoaming agent, and 80 parts by weight of water were uniformly mixed by a conventional method.

  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 2 kg / m ² (solid content). A concavo-convex pattern film (difference in level of the concavo-convex pattern: 1 to 3 mm) 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 2 kg / m ² (solid content). The concavo-convex pattern film 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 17, the evaluation of the contamination state was good both before and after promotion of Test 1, and good results were obtained in Test 2.

Claims (4)

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 pattern coating (B) has a concavo-convex pattern on the surface thereof, includes a resin component, a granular material, and a piperidine compound, and the ratio of the granular material to 100 parts by weight of the solid content of the resin component is 100 to 4000 parts by weight. And
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. 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) has a concavo-convex pattern on the surface thereof, and includes a resin component and a granular material to which a piperidine compound is bonded, and the ratio of the granular material to 100 parts by weight of the solid content of the resin component is 100 to 4000. Parts by weight,
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. 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 pattern coating (B) has a concavo-convex pattern on the surface thereof, includes a resin component, a granular material, and a piperidine compound to which a piperidine compound is bonded, and the ratio of the granular material to 100 parts by weight of the solid content of the resin component is 100 to 4000 parts by weight,
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 any one of claims 1 to 3.