JP2021066119A - tile - Google Patents

Abstract

To provide a novel tile that can employ a wide range of functional substances and maintains these functionalities for a long time.SOLUTION: A tile 1 has a tile body 3 having irregularities on a surface 3A, and a coating layer 5 formed on the tile body 3 surface 3A. The coating layer 5 has a resin 6 constituting a matrix, and particles 7 of a functional agent. An arithmetic average roughness Ra(μm) of the tile body 3 surface 3A and an average particle size d(μm) of the particles 7 satisfy a relational expression d<R.SELECTED DRAWING: Figure 1

Description

This disclosure relates to tiles.

Building materials carrying functional substances are known (see, for example, Patent Document 1). This building material is a decorative board, and is composed of a base material, a surface resin layer, a resin sheet, and a photocatalyst. In this decorative board, a recessed groove is formed on the surface of the resin sheet on the side where the photocatalyst is supported, and the photocatalyst is supported inside the recessed groove.

The following two methods can be considered when adding a function to a tile that is a building material. The first method is to add a functional substance to the glaze. The second method is a method of adding a functional substance to the paint and applying it.

Japanese Unexamined Patent Publication No. 2017-100443

Since the first method requires baking at a high temperature, it cannot be applied to an organic functional substance that burns at a high temperature, and is limited to the application of only an inorganic functional substance that does not burn at a high temperature. ..

In the second method, there are no restrictions on functional substances. In the second method, the coating film is easily worn, and when the coating film is worn, the function added by the functional substance is lost, that is, there is a problem related to the sustainability of the function.

The present disclosure is intended to solve at least a part of the above problems, and an object of the present disclosure is to provide a new tile that can be applied to a wide range of functional substances and has a high sustainability of function.

As a result of intensive research, we have developed a new tile. Based on this result, we will provide the following tiles.

It has a tile body having irregularities on its surface and a paint layer formed on the surface of the tile body, and the paint layer contains a resin constituting a matrix and particles of a functional agent. A tile in which the arithmetic mean roughness Ra (μm) of the surface of the tile body and the average particle diameter d (μm) of the particles satisfy the relational expression d <Ra.

It is sectional drawing which shows typically an example of the tile of an embodiment. It is a partially enlarged view of FIG. It is sectional drawing which shows typically the state after the wear of the tile of FIG. It is sectional drawing which shows typically an example of the tile of a reference form. It is sectional drawing which shows typically the state after the wear of the tile of FIG. It is sectional drawing which shows typically an example of the tile of an embodiment. It is sectional drawing which shows typically the state after the wear of the tile of FIG. It is sectional drawing which shows typically the conventional tile. It is sectional drawing which shows typically the state after the wear of the tile of FIG. It is a graph which shows the allergen reduction rate after the wear test of Experiment A. It is a graph which shows the ammonia gas reduction rate after the wear test of Experiment B. It is an observation image by SEM of the tile cross section.

1. 1. Tile 1
(1) Overall Structure The tile 1 has a tile body 3 having irregularities on the surface 3A and a paint layer 5 formed on the surface 3A of the tile body 3 (see FIG. 1). The paint layer 5 contains the resin 6 constituting the matrix and the particles 7 of the functional agent. The arithmetic mean roughness Ra (μm) of the surface 3A of the tile body 3 and the average particle diameter d (μm) of the particles 7 satisfy the following relational expression.
d <Ra

(2) Tile body 3
The tile body 3 has a base material 9. For the base material 9, for example, feldspar is used as a main raw material, clay, pottery stone, limestone, talc, etc. are mixed as necessary, and a molded product obtained by at least one of extrusion molding and press molding is fired. Manufactured by An example of the composition of the raw materials of the base material 9 is as follows.
Clay 20 parts by mass or more and 50 parts by mass or less Ceramic stone 0 parts by mass or more and 45 parts by mass or less Feldspar 20 parts by mass or more and 70 parts by mass or less

The tile body 3 may include a glaze portion 11 (glaze layer). When the glaze portion 11 is provided, the tile body 3 includes a base material 9 and a glaze portion 11 formed on the surface thereof. When the glaze portion 11 is not provided, the tile body 3 is made of a base material 9. In FIG. 1, the tile 1 in the case where the glaze portion 11 is provided is illustrated.

The glaze section 11 is formed by arbitrarily mixing and melting feldspar, silica stone, clay, limestone, talc, barium carbonate, frit and the like, and is made of glassy material containing some crystals.

The glaze portion 11 is formed by glazing the base material 9 with a spray, a curtain, a flow coater, or the like, and then firing the base material 9. The glaze portion 11 has sufficient adhesion due to fusion to the base material 9. In the tile 1 provided with the glaze portion 11, it is preferable that the unevenness of the surface 3A of the tile body 3 is formed by the glaze portion 11.

(3) Paint layer 5
The matrix of the paint layer 5 contains a resin as a main component. The main component refers to a substance having a content (% by mass) of 50% by mass or more. The resin is not particularly limited. As the resin, for example, one or more selected from the group consisting of acrylic resin, urethane resin, epoxy resin, acrylic silicon resin, acrylic urethane resin, fluororesin, alkyd resin, and silicon resin can be preferably used. The paint layer 5 is formed of a paint composition in which particles 7 are mixed with the paint constituting the matrix. The matrix of the paint layer 5 has a function of fixing the particles 7 of the functional agent to the tile body 3. The matrix of the paint layer 5 also has a function of protecting the functional agent particles 7 from external force by covering the functional agent particles 7.

The thickness of the paint layer 5 is not particularly limited. The thickness of the paint layer 5 is 1.0 μm with respect to the lower limit value from the viewpoint of sufficiently remaining the paint layer 5 containing the particles 7 and ensuring the function of the tile 1 even assuming wear in actual use. The above is preferable, and 3.0 μm or more is more preferable. The thickness of the paint layer 5 is preferably 20.0 μm or less, more preferably 15.0 μm or less, with respect to the upper limit value, from the viewpoint of maintaining the aesthetic appearance of the tile 1. The thickness of the coating layer 5 is preferably 1.0 μm or more and 20.0 μm or less, and more preferably 3.0 μm or more and 15.0 μm or less.

The thickness of the paint layer 5 can be measured by measuring the cross section of the tile 1 with a scanning electron microscope at a magnification of 2000 times. Specifically, it can be obtained by measuring any three points in the cross section and taking the average value of the thicknesses of the three measured points.

(4) Functional agent particles 7
The type of functional agent is not particularly limited. The functional agent may be either an organic functional agent or an inorganic functional agent. The functional agent is preferably one or more selected from the group consisting of antiallergen agents, deodorants, antibacterial agents, antiviral agents, fungicides, algae repellents, insect repellents, and photocatalysts. The anti-allergen agent is not particularly limited. As the anti-allergen agent, for example, polyphenol-based polymers such as poly (4-vinylphenol) and poly (vinyl 4,5-hydroxybenzoate) are preferably exemplified. As a commercially available anti-allergen agent, an allerbuster (trade name) manufactured by Sekisui Material Solutions Co., Ltd. can be used. Anti-allergen agents are those that act effectively against various allergens such as mites and pollen.

The state of existence of the functional agent particles 7 in the coating layer 5 is not particularly limited. The particles 7 of the functional agent may be uniformly dispersed in the coating layer 5. The particles 7 of the functional agent may be settled in the lower part of the coating layer 5. It is preferable that the functional agent particles 7 are not unevenly distributed on the surface layer of the paint layer 5.

The density of the functional agent is not particularly limited. It is preferable that the density of the functional agent is equal to or higher than the density of the paint for forming the paint layer 5. When the density of the functional agent is "SG1" and the density of the paint for forming the paint layer 5 is "SG2", it is preferable to satisfy the following relational expression (1).
SG1 ≥ SG2 ... Relational expression (1)

Normally, when the tile body 3 is painted, the tile body 3 is in a state where the surface 3A is facing upward. In this case, if the above relational expression (1) is satisfied, the particles 7 of the functional agent settle and easily enter the recess 13, providing the tile 1 having high sustainability of the function (see FIG. 1). On the other hand, when the above relational expression (1) is not satisfied, the particles 7 of the functional agent float up, and the particles 7 of the functional agent tend to gather on the surface of the paint layer 5 (see FIG. 6). In this case (when the relational expression (1) is not satisfied), the particles 7 of the functional agent are easily removed due to wear (see FIG. 7). For this reason, it is preferable to satisfy the relational expression (1).

(5) Relationship between the Arithmetic Mean Roughness Ra of the Surface 3A of the Tile Body 3 and the Average Particle Diameter d of the Particles 7 In the tile 1 of the present disclosure, the Arithmetic Mean Roughness Ra (μm) of the surface 3A and the average of the particles 7 are used. The particle size d (μm) satisfies the following relational expression (2).
d <Ra ... Relational expression (2)

The reason why it is presumed that the sustainability of the function is increased when this relational expression (2) is satisfied will be described with reference to FIGS. 1, 3, 4, and 5. In the case of the tile 1 of the embodiment of FIG. 1, even if the tile 1 is worn to the state of FIG. 3, the functional agent particles 7 that have entered the recess 13 of the surface 3A remain. That is, even if the surface of the tile 1 is rubbed against an object such as a shoe sole and worn during use, the object is blocked by the convex portion 15 and is less likely to enter the concave portion 13. The functional agent particles 7 that have entered the recess 13 are likely to remain protected from the object in this way. In the case of tile 1 of the embodiment, it is presumed that the function is sustained by the remaining functional agent particles 7. On the other hand, in the case of tile 1 in the reference form of FIG. 4, d ≧ Ra. In the case of this tile 1, when it is worn, the particles 7 of the functional agent are removed. As shown in FIG. 5, after abrasion, the possibility that the particles 7 of the functional agent remain is low, and it is considered that the function is not maintained. For this reason, it is preferable that at least a part of the particles 7 is present in the recess 13 of the surface 3A of the tile body 3. "Existing in the recess 13 of the surface 3A of the tile body 3" means the following. When observing the cross section of the tile 1, it means that some particles 7 are present on the hem side (lower side of FIG. 2) with respect to the line L connecting the tops 15A of the adjacent convex portions 15.

The arithmetic mean roughness Ra of the surface 3A of the tile body 3 can be appropriately changed according to the average particle diameter d of the particles 7. The arithmetic mean roughness Ra is preferably 1.0 μm or more, more preferably 2.0 μm or more, with respect to the lower limit value, from the viewpoint of the slip resistance of the tile. The arithmetic mean roughness Ra is preferably 15.0 μm or less, more preferably 10.0 μm or less, with respect to the upper limit value from the viewpoint of stain resistance and touch. The arithmetic mean roughness Ra is preferably 1.0 μm or more and 15.0 μm or less, and more preferably 2.0 μm or more and 10.0 μm or less.

The arithmetic mean roughness Ra of the surface 3A of the tile body 3 can be controlled by at least one of the adjustment of the base material 9 and the adjustment of the glaze portion 11. Examples of the adjustment of the base material 9 include adjustment of the particle size of the ceramic powder. Examples of the adjustment of the glaze unit 11 include adjustment of the viscosity of the glaze raw material, adjustment of the coating amount, and the like.

The average particle diameter d of the particles 7 can be appropriately changed according to the arithmetic mean roughness Ra of the surface 3A of the tile body 3. The average particle size d is preferably 15 μm or less, more preferably 10 μm or less, with respect to the upper limit value from the viewpoint of maintaining the aesthetic appearance of the tile. The average particle size d is larger than 0 μm.

The arithmetic mean roughness Ra (μm) can be measured, for example, under the following measurement conditions.
[Arithmetic mean roughness measurement conditions]
Measuring machine: Surface roughness contour shape measuring machine "surfcom1800G" manufactured by Tokyo Seimitsu Co., Ltd.
Measuring distance: 12.5mm
Measurement speed: 0.15 mm / s
Measurement range: ± 128.0 μm
Cutoff wavelength: 2.5 mm
Measurement type: Roughness measurement Measuring needle: 2 μm R standard pickup Cutoff type: Gaussian tilt correction: Least squares Straight line standard: JIS B0601: 2001

The average particle diameter d of the particles 7 can be measured under the following measurement conditions. Arithmetic mean of 5 or more fields of view when either the surface of the coating film or the cross section is observed with a scanning electron microscope at a magnification of 500 to 5000 and the maximum length (major axis) of 10 arbitrary particles in the field of view is measured. Is the value of.

(6) Method for Manufacturing Tile 1 Tile 1 is manufactured by, for example, the following method. Clay, feldspar, pottery stone, etc., which are the raw materials of the tile body 3, are crushed with a ball mill or the like, adjusted to a moisture content of 4% or more and 9% or less with a spray dryer or the like, granulated, and pressure-molded with a dry press or the like. It is made into a body, and this molded product is dried. After that, the glaze is applied to the molded body by a method such as spraying, curtaining, or a roll coater, and the tile body 3 having the glaze portion 11 is formed by firing at 1000 ° C. or higher and 1300 ° C. or lower. Particles 7 of the functional agent are mixed with the acrylic paint and dispersed by stirring to prepare a paint composition. The tile 1 on which the paint layer 5 is formed can be obtained by applying the paint composition to the surface of the tile body 3 by a method such as spraying or a roller, drying and curing the paint composition.

2. Effects and Applications of Tile 1 According to the present disclosure, a new tile 1 having a high sustainability of function is provided. When the conventional tile 100 illustrated in FIG. 8 is worn to the state shown in FIG. 9, the particles 7 of the functional agent are removed. On the other hand, in the case of the tile 1 of the embodiment, even if the tile 1 is worn and the state shown in FIG. 3 is obtained, the functional agent particles 7 that have entered the recess 13 of the surface 3A remain, so that the function is maintained.

The tile 1 of the present disclosure has excellent anti-allergen performance, deodorant property, etc. for a long period of time by immobilizing particles 7 of functional agents such as anti-allergen agent and deodorant and having excellent durability. The tile 1 is preferably used as an interior material in a building such as a house. The tile 1 of the present disclosure is particularly preferably used as a flooring material for living rooms, bathrooms, kitchens, etc., which are often touched by humans with bare skin.

Hereinafter, a more specific description will be given with reference to Examples. Experiment A using an anti-allergen agent as a functional agent, Experiment B using a deodorant as a functional agent, and Experiment C using an antibacterial agent as a functional agent will be described.

1. 1. Preparation of evaluation sample (1) Tile body Table 1 is a table relating to Experiment A. Table 2 is a table relating to Experiment B. As shown in Tables 1 and 2, tiles having different surface arithmetic mean roughness Ra (μm) (manufactured by LIXIL Corporation) were used as the tile body. In these tiles, the surface roughness of the glaze portion is adjusted. By adjusting the amount of glaze applied, the glaze coating method (curtain, spray), the flow rate during spray coating, the air ratio, the nozzle diameter, etc., these tiles have an arithmetic average roughness Ra on the surface of the glaze. The values are adjusted so as to be shown in Tables 1 and 2. In Experiment C, tiles with an arithmetic mean roughness Ra of 12.8 μm were used. The arithmetic mean roughness Ra was measured by the method described above.

(2) Preparation of paint composition (2.1) Experiment A
The coating composition forming the coating layer was prepared by mixing and stirring the following functional agent particles with the following coating material. The mixing ratio of the paint and the functional agent particles was such that the solid content ratio of the two was 25: 4 (mass standard).

〔paint〕
Ingredients: Acrylic resin emulsion Product name: Polysol AP-3900
Manufacturer: Showa Denko KK
Density: 1.0 g / cm ³ or more and 1.1 g / cm ³ or less

[Functional agent particles Anti-allergen agent]
Product name: Allele Buster T
Manufacturer: Sekisui Material Solutions Co., Ltd. Average particle size: 0.14 μm
Density: 1.1 g / cm ³ or more and 1.5 g / cm ³ or less

(2.2) Experiment B
The coating composition forming the coating layer was prepared by mixing and stirring the following functional agent particles with the following coating material. The mixing ratio of the paint and the functional agent particles was such that the solid content ratio of the two was 25: 4 (mass standard).

〔paint〕
Ingredients: Acrylic resin emulsion Product name: Polysol AP-3900
Manufacturer: Showa Denko KK
Density: 1.0 g / cm ³ or more and 1.1 g / cm ³ or less

[Functional agent particle deodorant]
Product name: Kesmon NS-10
Manufacturer: Toagosei Co., Ltd. Average particle size: 1.0 μm

(2.3) Experiment C
The coating composition forming the coating layer was prepared by mixing and stirring the following functional agent particles with the following coating material. The mixing ratio of the paint and the functional agent particles was such that the solid content ratio of the two was 25: 4 (mass standard).

〔paint〕
Ingredients: Acrylic resin emulsion Product name: Polysol AP-3900
Manufacturer: Showa Denko KK
Density: 1.0 g / cm ³ or more and 1.1 g / cm ³ or less

[Functional agent particle antibacterial agent (inorganic antibacterial agent)]
Product name: Novalon VZ200
Manufacturer: Toagosei Co., Ltd. Average particle size: 3 μm

(3) Method for producing test specimen (evaluation sample) A coating composition ^{was spray-coated on each tile body at 33 g / m 2} (solid content 8.8% (mass standard)) and dried to form a coating layer. Each test piece was prepared in this way.

2. Evaluation In Experiment A, anti-allergenicity was evaluated before and after the wear test. The wear test and anti-allergenicity evaluation were performed as follows. In Experiment B, deodorant property evaluation was performed before and after the wear test. The wear test and deodorant property evaluation were performed as follows. In Experiment C, the test piece was cut and the cut surface was observed with a scanning electron microscope (SEM).

(1) Wear test (common to experiments A and B)
A rag soaked in water and squeezed tightly was placed on a 100 mm × 100 mm test piece, and the test piece was slid 1500 times by a wear test device while applying a load through a sponge with a weight of 500 g. The test was conducted while constantly supplying a constant amount of water so that the rag would not dry out during the test.

(2) Anti-allergen evaluation 100 μL of a commercially available mite allergen aqueous solution “Der f 1” (Tokyo Environmental Allergen Research Institute Co., Ltd.) was dropped onto the surface of the test piece and left for 1 hour, and then the mite allergen on the surface of the test piece. The amount of mite allergen was measured according to an enzyme-linked immunosorbent assay (ELISA method), and the antiallergen property was evaluated.

(3) Deodorant evaluation The test piece was cut into 30 mm × 30 mm, and these surfaces were covered with aluminum tape in order to avoid adsorption to the side surfaces and the bottom surface. The test piece was sealed in a Tedlar (registered trademark) bag, and 3 L of ammonia gas adjusted to 30 ppm was put therein. After 5 hours, the ammonia gas concentration was measured using a detector tube type gas measuring device (Gastec Co., Ltd.), and the reduction rate from the initial concentration was calculated.

(4) Observation by SEM Observation by SEM was performed under the following measurement conditions.
<Measuring equipment>
Measuring equipment: Electron microscope (SEM)
Company: Hitachi High-Tech Fielding Co., Ltd. Part No .: S-3400N
<Measurement conditions>
Acceleration voltage: 15kV
Observation mode: Reflected electron image, low vacuum mode Working distance: 10 mm
Magnification: 500 times

3. 3. Evaluation result (1) Experiment A
The results are shown in Table 1 and FIG. The vertical axis of the graph of FIG. 10 shows the allergen reduction rate (%) measured after the wear test, and the horizontal axis shows the arithmetic mean roughness Ra of the surface of the tile body (the surface of the glaze portion). As can be seen from Table 1 and FIG. 10, in Experimental Examples 2 to 6 in which the arithmetic average roughness Ra of the tile body is larger than the average particle diameter d of the functional agent particles, the allergen reduction rate is the initial value even after the wear test. It maintains the same 80% to 90% level. On the other hand, in Experimental Example 1 in which the arithmetic average roughness Ra of the tile body is smaller than the average particle size d of the functional agent particles, it can be confirmed that the allergen reduction rate is significantly reduced after the wear test. From this result, it was confirmed that the function can be maintained for a long period of time by satisfying d <Ra in the relationship between the functional agent particles and the surface roughness of the tile body.

(2) Experiment B
The results are shown in Table 2 and FIG. The vertical axis of the graph of FIG. 11 shows the ammonia gas reduction rate (%) measured after the wear test, and the horizontal axis shows the arithmetic mean roughness Ra of the surface of the tile body (the surface of the glaze portion). As can be seen from Table 2 and FIG. 11, in Experimental Examples 9 to 14 in which the arithmetic average roughness Ra of the tile body is larger than the average particle diameter d of the functional agent particles, the ammonia gas reduction rate is the initial value even after the wear test. The 90% level, which is the same as the above, is generally maintained. On the other hand, in Experimental Examples 7 to 8 in which the arithmetic average roughness Ra of the tile body is smaller than the average particle size d of the functional agent particles, it can be confirmed that the ammonia gas reduction rate is significantly reduced after the wear test. From this result, it was confirmed that the function can be maintained for a long period of time by satisfying d <Ra in the relationship between the functional agent particles and the surface roughness of the tile body.

(3) Experiment C
FIG. 12 shows an observation image by SEM. It was confirmed that the functional agent particles were gathered in the recesses on the surface of the tile body.

Not limited to the embodiments and examples detailed above, various modifications and changes are possible.

1 ... tile, 3 ... tile body, 3A ... surface, 5 ... paint layer, 6 ... resin constituting matrix, 7 ... particles, 9 ... base material, 11 ... glaze part, 13 ... concave part, 15 ... convex part, 100 … Conventional tiles

Claims (4)

The tile body with irregularities on the surface and
With a paint layer formed on the surface of the tile body,
The coating layer contains the resin constituting the matrix and the particles of the functional agent.
A tile in which the arithmetic mean roughness Ra (μm) of the surface of the tile body and the average particle diameter d (μm) of the particles satisfy the relational expression d <Ra. The tile according to claim 1, wherein at least a part of the particles is present in a recess on the surface of the tile body. The tile according to any one of claims 1 and 2, wherein the arithmetic mean roughness Ra is 1.0 μm or more and 15.0 μm or less. The tile according to any one of claims 1 to 3, wherein the average particle diameter d is 15 μm or less.

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