JP2013234560A - Decorative wall surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress progress of contamination and maintain initial beauty for a long period of time in a decorative wall surface having a decorative coating film provided with an uneven pattern formed by a joint.SOLUTION: The decorative wall surface comprises: a substrate; a colored coating film (A); a patterned coating film (B) partitioned by a joint; and a transparent coating film (C) in this order. The patterned coating film (B) contains a resin component and a granular material so that a ratio of the granular material with respect to 100 pts. wt. of a solid part of the resin component becomes 100-4,000 pts. wt., and further contains a piperidine compound. The transparent coating film (C) contains silica having an average primary particle diameter of 1-200 nm and a resin component.

Description

  The present invention relates to a decorative wall surface in a building, a civil engineering structure, or the like.

Conventionally, a decorative film having a three-dimensional uneven pattern is formed on a wall surface of a building, a civil engineering structure, or the like. As one type of such a decorative film, there is one provided with an uneven pattern by joints.
For example, Patent Document 1 describes a method in which a joint material is applied to a surface to be coated, a spray material is applied, and then the joint material is removed to form an uneven pattern by the joint. Patent Document 2 describes that a pattern is further applied to a convex region of a concavo-convex pattern divided by joints by 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, joints that become concave and convex portions tend to be contaminated. If contaminants accumulate in such joints, there is a risk of fouling the decorative coating.

Japanese Patent Laid-Open No. 10-266517 Japanese Patent Application Laid-Open No. 8-3333861

  The present invention has been made in view of the above-described problems, and suppresses the progress of contamination in a decorative wall surface having a decorative coating provided with unevenness by joints, and maintains the initial aesthetics for a long period of time. It is for the purpose.

  As a result of intensive studies to achieve the above object, the present inventor has conceived that a colored film (A), a specific pattern film (B), and a specific transparent film (C) are provided. It came to complete.

That is, the present invention has the following characteristics.
1. A decorative wall surface provided with a decorative film on a base material,
As the decorative coating, a colored coating (A), a patterned coating (B) partitioned by joints, and a transparent coating (C) are provided in order on the base material,
The pattern coating (B) 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.
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 provided with a decorative film on a base material,
As the decorative coating, a colored coating (A), a patterned coating (B) partitioned by joints, and a transparent coating (C) are provided in order on the base material,
The pattern coating (B) includes a resin component to which a piperidine compound is bonded, and a powder, and the ratio of the powder to a solid content of 100 parts by weight 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 provided with a decorative film on a base material,
As the decorative coating, a colored coating (A), a patterned coating (B) partitioned by joints, and a transparent coating (C) are provided in order on the base material,
The pattern coating (B) 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.
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.
5. The colored coating (A) has a piperidine compound. ~ 4. The decorative wall surface according to any one of the above.

  ADVANTAGE OF THE INVENTION According to this invention, in the makeup | decoration wall surface which has a decorative film by which the uneven | corrugated pattern by the joint was given, progress of contamination can be suppressed and the initial aesthetics can be maintained over a long period of time.

It is a figure (sectional view) showing an example of the present invention. It is a figure which shows the process for forming an example of this invention.

1: Substrate 2: Colored coating (A)
3: Joint material 4: Pattern coating (B)
5: Transparent coating (C)

  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 a base material.
As a base material, it constitutes a wall surface of a building, a civil engineering structure, etc., for example, concrete, mortar, siding board, extruded board, gypsum board, perlite board, plywood, brick, plastic board, metal board, Examples include glass and porcelain tiles. 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.), and has already been provided with a film, or has been applied with wallpaper. Also good.

  In the present invention, a colored coating (A), a patterned coating (B), and a transparent coating (C) are provided on the surface of the substrate as a decorative coating. An example is shown in FIG. Of these, the patterned coating (B) contains a resin component and powder and further has 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 coating, it is possible to impart a concavo-convex pattern by joints, suppress the progress of contamination of the decorative coating, and maintain the initial aesthetics 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). In the present invention, it is presumed that the effect of maintaining aesthetics is sufficiently exhibited by these synergistic actions.

[Colored coating (A)]
The colored coating (A) is a coating that appears as a joint of the decorative coating of the present invention and expresses the joint color.
As such a colored coating (A), for example, a coating containing a resin component and a coloring pigment can be used.

  Examples of the resin component in the colored coating (A) include acrylic resin, urethane resin, vinyl acetate resin, silicon resin, fluororesin, acrylic vinyl acetate resin, acrylic urethane resin, and acrylic silicon resin. Or 2 or more types can be used. Among these, acrylic resin, acrylic silicon resin, and the like are preferable.

  In the colored coating (A), color matching may be appropriately performed using a coloring pigment. At this time, if the color tone of the colored coating (A) is set to a hue (co-color) that approximates the pattern coating (B) described later, the overall finish is uniform. Further, if the color tone of the colored coating (A) is set to a hue different from that of the pattern coating (B), the contrast between the joint color and the pattern coating (B) becomes a clear finish.

Examples of color pigments include titanium oxide, zinc oxide, carbon black, lamp black, bone black, graphite, black iron oxide, copper chrome black, cobalt black, copper manganese iron black, red potato, molybdate orange, permanent red, and permanent. Carmine, anthraquinone red, perylene red, quinacridone red, yellow iron oxide, titanium yellow, first yellow, benzimidazolone yellow, chrome green, cobalt green, phthalocyanine green, ultramarine, bitumen, cobalt blue, phthalocyanine blue, quinacridone violet, dioxazine Violet etc. are mentioned, These 1 type (s) or 2 or more types can be used.
The ratio of the color pigment is preferably 1 to 300 parts by weight, more preferably 2 to 200 parts by weight with respect to 100 parts by weight of the solid content of the resin component.

The colored coating (A) can be formed by applying and drying a coating material containing the above components (hereinafter also referred to as “coating material A”).
As this coating material A, what has a resin component, a color pigment, and a piperidine compound is suitable. If the coating material A is such an aspect, the colored coating (A) will have a piperidine compound, and the adhesion between the colored coating (A) and the transparent coating (C) will be maintained at the joint for a long period of time. It is suitable in terms of holding.

As the piperidine compound in the colored coating (A), 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 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 coating 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 matting agents, aggregates, thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreezing agents, pH adjusting agents, antiseptics, antifungal agents, Examples include algal agents, antibacterial agents, dispersants, antifoaming agents, adsorbents, fibers, crosslinking agents, ultraviolet absorbers, antioxidants, and catalysts.

[Pattern film (B)]
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, uneven patterns due to joints are 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, and the same compounds as in the above (A) can be used.
As the form of this piperidine compound, as in the above (A),
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 those exemplified for the colored coating (A). These can 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, and examples thereof include those exemplified for the colored coating (A). 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 a coating material containing the above components (hereinafter also referred to as “coating material B”). 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.

[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 a coating material containing the above components (hereinafter also referred to as “coating material C”). 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.

[Method of forming decorative wall surface]
The decorative wall surface of the present invention is obtained by sequentially providing a colored coating (A), a patterned coating (B) partitioned by joints, and a transparent coating (C) on a substrate. Such a decorative wall surface can be formed, for example, by the following process as shown in FIG.
(1) A step of applying a coating material A to a base material to form a colored film (A);
(2) A step of attaching a joint material to the surface of the colored coating (A),
(3) A step of applying the coating material B to the surface obtained in (2) above,
(4) a step of detaching part or all of the joint material;
(5) The process of applying the coating material C on the surface obtained in (4) above

In the said process (1), when apply | coating the coating | covering material A with respect to a base material, well-known coating instruments, such as a brush, a roller, and a spray, can be used, for example. The coating amount of the coating material A is preferably about 0.05 to ² kg / m ^{2 in} terms of solid content.

  As the joint material in the step (2), joint rods, joint tapes, inset joint materials, joint pattern papers and the like can be used. Examples of the material for the joint material include various resins, rubbers, resin foams, papers, and the like. Although the timing which affixes such a joint material on the surface of a colored film (A) is not specifically limited, After the colored film (A) dries, it is preferable. Moreover, an adhesive agent, an adhesive, etc. can be used for sticking a joint material as needed.

  What is necessary is just to determine the position, space | interval, etc. which paste a joint material according to a desired joint pattern. For example, it can be affixed at equal intervals or can be affixed randomly. Examples of patterns include tile-like patterns, brick-like patterns, geometric patterns, polka dot patterns, striped patterns, lattice patterns, swirl patterns, heraldic patterns, as well as graphic patterns designed for animals, plants, objects, characters, etc. Is possible. In order to express these patterns, a plurality of linear joint materials may be used in combination, or a flat pattern paper punched according to the pattern shape may be used as the joint material. The width of the joint material is preferably about 0.5 to 100 mm, and the height of the joint material is preferably about 0.5 to 10 mm.

In the step (3), when the coating material B is applied, a coating method may be selected as appropriate. For example, a spray, a roller, a brush, a trowel, or the like can be used as the coating instrument. If necessary, a plurality of these painting instruments may be used in combination.
The coating amount of the coating material B is preferably about 0.5 to 8 kg / m ^{2 in} terms of solid content.

In the above step (4), the timing for detaching the joint material is not particularly limited as long as a desired joint can be formed, and the coating material B may be in an uncured state or in a cured state. .
In addition, when using joint rods, joint tapes, etc. as joint materials, all of the joint materials may be removed, and when fitting type joint materials are used as joint materials, a part of the joint materials may be removed. Good.

In the step (5), the covering material C may be applied to the entire surface. As a result, a transparent coating (C) is formed on the colored coating (A) at the joint, and a decorative coating in which the pattern coating (B) and the transparent coating (C) are laminated on the colored coating (A) in the other regions. can get.
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 for 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
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) .8 wt%), glass transition temperature 2 ° C., solid content 50 wt%} for 200 parts by weight of calcium carbonate 240 parts by weight, titanium oxide 20 parts by weight, film-forming aid 6 parts by weight, viscosity modifier 3 parts by weight 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 A2
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 0.8% by weight), glass transition temperature 2 ° C., solid content 50% by weight} 200 parts by weight, 240 parts by weight of calcium carbonate, 20 parts by weight of titanium oxide, 6 parts by weight of film-forming aid, 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 A3
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, 6 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 A4
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, film forming aid 6 parts by weight, viscosity modifier 3 parts by weight, antifoaming agent 2 parts by weight, and water 80 parts by weight were uniformly mixed by a conventional method.

○ Coating material A5
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, 6 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 80 parts by weight of water were uniformly mixed by a conventional method.

○ Coating material A6
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, 6 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 80 parts by weight of water were uniformly mixed by a conventional method.

○ Coating material A7
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, 6 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 80 parts by weight of water were uniformly mixed by a conventional method.

○ Coating material A8
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) 0.02%), glass transition temperature 2 ° C., solid content 50% by weight} to 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, 6 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 A9
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) 0.02%), glass transition temperature 2 ° C., solid content 50% by weight} to 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, 6 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 A10
Acrylic resin 5 {water dispersible resin obtained by emulsion polymerization of acrylic monomer (not including polymerizable piperidine compound), glass transition temperature 2 ° C, solid content 50 wt%} 200 parts by weight of calcium carbonate 240 weights 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 6 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 A11
For 200 parts by weight of acrylic resin 5 (same as above), 240 parts by weight of calcium carbonate, 20 parts by weight of titanium oxide, 6 parts by weight of film-forming aid, 3 parts by weight of viscosity modifier, 2 parts by weight of antifoaming agent, 80 parts of water The parts by weight were uniformly mixed by a conventional method.

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

○ Coating material B1
Acrylic resin 6 {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) 5% by weight), glass transition temperature 5 ° C., solid content 50% by weight} with respect to 200 parts by weight, colored silica sand (a mixture of brown silica sand, red silica sand and light yellow silica sand, average particle size 0.08 to 0.2 mm) 420 parts by weight, 10 parts by weight of a film-forming aid, 4 parts by weight of a thickener, and 2 parts by weight of an antifoaming agent were uniformly mixed by a conventional method.

○ Coating material B2
Acrylic resin 7 (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 Medium weight 0.5%), glass transition temperature 5 ° C., solid content 50% by weight} to 200 parts by weight, colored silica sand (a mixture of brown silica sand, red silica sand and light yellow silica sand, average particle size 0.08-0. 2 mm) 420 parts by weight, a film-forming aid 10 parts by weight, a thickener 4 parts by weight, and an antifoaming agent 2 parts by weight were uniformly mixed by a conventional method.

○ Coating material B3
2 parts by weight of piperidine compound {bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate}, 200 parts by weight of acrylic resin 6 (same as above), colored silica sand (brown silica sand and red silica sand) A mixture of light yellow silica sand, average particle diameter 0.08 to 0.2 mm) 420 parts by weight, film forming aid 10 parts by weight, thickener 4 parts by weight, and antifoaming agent 2 parts by weight were uniformly mixed by a conventional method. .

○ Coating material B4
2 parts by weight of piperidine compound {decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester compound} per 200 parts by weight of acrylic resin 6 (same as above) , 420 parts by weight of colored silica sand (a mixture of brown silica sand, red silica sand and light yellow silica sand, average particle size 0.08 to 0.2 mm), 10 parts by weight of a film-forming aid, 4 parts by weight of a thickening agent, 2 defoamers The parts by weight were uniformly mixed by a conventional method.

○ Coating material B5
Piperidine compound {bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate} 1 part by weight, colored silica sand (brown silica sand and red silica sand) with respect to 200 parts by weight of acrylic resin 6 (same as above) A mixture of light yellow silica sand, average particle diameter 0.08 to 0.2 mm) 420 parts by weight, film forming aid 10 parts by weight, thickener 4 parts by weight, and antifoaming agent 2 parts by weight were uniformly mixed by a conventional method. .

○ Coating material B6
Piperidine compound {bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate} 4 parts by weight, colored silica sand (brown silica sand and red silica sand) with respect to 200 parts by weight of acrylic resin 6 (same as above) A mixture of light yellow silica sand, average particle diameter 0.08 to 0.2 mm) 420 parts by weight, film forming aid 10 parts by weight, thickener 4 parts by weight, and antifoaming agent 2 parts by weight were uniformly mixed by a conventional method. .

○ Coating material B7
Piperidine compound {bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate} 8 parts by weight, colored silica sand (brown silica sand and red silica sand) with respect to 200 parts by weight of acrylic resin 6 (same as above) A mixture of light yellow silica sand, average particle diameter 0.08 to 0.2 mm) 420 parts by weight, film forming aid 10 parts by weight, thickener 4 parts by weight, and antifoaming agent 2 parts by weight were uniformly mixed by a conventional method. .

○ Coating material B8
Acrylic resin 8 {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) 0.02%), glass transition temperature 5 ° C., solid content 50% by weight} 200 parts by weight, piperidine compound {bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate} 2 parts by weight , 420 parts by weight of colored silica sand (a mixture of brown silica sand, red silica sand and light yellow silica sand, average particle size 0.08 to 0.2 mm), 10 parts by weight of a film-forming aid, 4 parts by weight of a thickening agent, 2 defoamers The parts by weight were uniformly mixed by a conventional method.

○ Coating material B9
Acrylic resin 9 {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) 0.02%), glass transition temperature 5 ° C., solid content 50% by weight} 200 parts by weight, piperidine compound {bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate} 2 parts by weight , 420 parts by weight of colored silica sand (a mixture of brown silica sand, red silica sand and light yellow silica sand, average particle size 0.08 to 0.2 mm), 10 parts by weight of a film-forming aid, 4 parts by weight of a thickening agent, 2 defoamers The parts by weight were uniformly mixed by a conventional method.

○ Coating material B10
Acrylic resin 10 {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} with respect to 200 parts by weight, piperidine compound (bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate) 2 parts by weight, colored silica sand (a mixture of brown silica sand, red silica sand and light yellow silica sand, average particle size 0.08 to 0.2 mm) 420 Part by weight, 10 parts by weight of a film-forming aid, 4 parts by weight of a thickener and 2 parts by weight of an antifoaming agent were uniformly mixed by a conventional method.

○ Coating material B11
Acrylic resin 11 {Water-dispersible resin obtained by emulsion polymerization of acrylic monomer (not including polymerizable piperidine compound), glass transition temperature 5 ° C., solid content 50 wt%} A mixture of 420 parts by weight of a mixture of silica sand, red silica sand and light yellow silica sand, average particle size 0.08 to 0.2 mm), 10 parts by weight of a film-forming aid, 4 parts by weight of a thickener, and 2 parts by weight of an antifoaming agent. To mix evenly.

  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 0.8 kg / m ² (solid content), and after curing for 6 hours, stick-shaped joint material (joint width 10 mm, height 5 mm, made of polyethylene) is an adhesive. And stuck in a lattice shape. Subsequently, the coating material B was spray-coated at a coating amount of 2 kg / m ² (solid content), and the rod-shaped joint material was desorbed before the coating was dried. 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. The coating and curing were all 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 results)
Table 1 shows the coating materials used in the above test and the test results. In Examples 1 to 27, the evaluation of the contamination state was good before and after the promotion of the test.

Claims (5)

A decorative wall surface provided with a decorative film on a base material,
As the decorative coating, a colored coating (A), a patterned coating (B) partitioned by joints, and a transparent coating (C) are provided in order on the base material,
The pattern coating (B) 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.
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 provided with a decorative film on a base material,
As the decorative coating, a colored coating (A), a patterned coating (B) partitioned by joints, and a transparent coating (C) are provided in order on the base material,
The pattern coating (B) includes a resin component to which a piperidine compound is bonded, and a powder, and the ratio of the powder to a solid content of 100 parts by weight 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 provided with a decorative film on a base material,
As the decorative coating, a colored coating (A), a patterned coating (B) partitioned by joints, and a transparent coating (C) are provided in order on the base material,
The pattern coating (B) 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.   The said colored film (A) has a piperidine compound, The decorative wall surface in any one of Claims 1-4.

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