JP2024001734A - Plumbing component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plumbing component having both good antiviral property and durability.

SOLUTION: A plumbing component includes a base material, and a surface layer provided on the base material, wherein the surface layer contains an acrylic resin, particles and an inorganic antiviral agent as main components, the particles are particles containing a (meth)acrylic resin as a main component, the inorganic antiviral agent contains an inorganic carrier and an inorganic active ingredient carried on the inorganic carrier, and a ratio of the volume of the inorganic antiviral agent included in a region (hereinafter referred to as "target region") above the particles at least partially included in a region (hereinafter referred to as "2 μm region") between the outermost surface of the surface layer and a position with a depth of 2 μm in a direction vertical to the base material direction from the outermost surface, to the volume of the region between the outer surface of the surface layer and the position with a depth of 2 μm in a direction vertical to the base material direction from the outermost surface is 20% or more.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2024,JPO&INPIT

Description

TECHNICAL FIELD The present invention relates to a plumbing member. Specifically, the present invention relates to a plumbing member that has both antiviral properties and durability.

In order to impart a desired function to a plumbing member, it has been conventional practice to provide a surface layer having the desired function on the surface of a base material of the plumbing component. There is a possibility that pathogens such as viruses may adhere to the surfaces of plumbing components, and people touch the surfaces of plumbing components with their hands, so plumbing components are required to have good hygiene. On the other hand, in order to maintain hygiene, plumbing members are frequently cleaned, and the surfaces thereof are subjected to loads (for example, sliding force) caused by cleaning. For this reason, water-related members are required to have performance (durability) that can withstand the load.

For example, JP2014-233946A (Patent Document 1) describes a member in which a hydrophilic surface layer is formed on a base material, and that the surface layer includes particles of a specific size. (scope of claims, etc.) Specifically, it is described that the surface layer contains methacrylate having a sulfonic acid group and acrylic resin beads in a coating film mainly composed of acrylic resin (Examples 1 to 3). 5). According to Patent Document 1, particles such as acrylic resin beads are said to impart anti-slip properties to the surface layer (paragraphs 0026, 0029, etc.). Furthermore, JP 2015-212324A (Patent Document 2) proposes a paint for further improving the hydrophilicity of the surface layer of plumbing products (paragraph 0007, etc.). By blending a volatile compound having a polymerizable group and a hydrophilic group (for example, hydroxymethyl methacrylate (HEMA)) with methacrylate having a sulfonic acid group, the methacrylate having a sulfonic acid group can be used in the coating film manufacturing process. It has been proposed that segregation to the coating surface is promoted, resulting in higher hydrophilicity.

JP 2019-60119 A (Patent Document 3) describes a flooring material having an outermost surface layer, and this outermost layer contains urethane acrylate as a main component and inorganic particles (silica particles) as a particle component. It is specifically described that it contains resin beads (urethane beads) and an antibacterial agent (Ag-Cu compound) (paragraph 0062). According to Patent Document 1, resin beads that are harder than urethane acrylate impart wear resistance to flooring materials (paragraph 0029, etc.), and inorganic particles impart matte properties to flooring materials (paragraph 0025, etc.). ).

JP-A No. 11-48412 (Patent Document 4) describes providing an antibacterial protective layer on the surface of a decorative material (claim 3, etc.), and this protective layer consists of polyether urethane as a main component. It is specifically described that it contains acrylate, a spherical filler (silica), and a spherical antibacterial agent (paragraph 0064). According to Patent Document 2, a decorative material with excellent wear resistance can be obtained by using spherical fillers and antibacterial agents (paragraph 0007, etc.). Moreover, according to FIGS. 2, 3, and 5 of Patent Document 2, it is understood that both the spherical filler and the spherical antibacterial agent exist in a uniformly dispersed state within the protective layer.

JP 2018-202835A (Patent Document 5) discloses a decorative board including an organic resin layer (visible light reflective layer) on a base material, in which a part of the organic resin layer is buried in the layer. , a decorative board is described in which photocatalyst-supporting particles exist with the remainder exposed outside the layer, and a visible light-responsive photocatalyst is supported on the exposed surface of the photocatalyst-supporting particles (Claims, Figure 2 etc). According to Patent Document 3, by embedding a part of the photocatalyst-supporting particles in the organic resin layer, the adhesion between the organic resin layer and the photocatalyst-supporting particles is ensured, and the photocatalyst-supporting particles are embedded outside the organic resin layer. It is said that by exposing the remainder of the virus and supporting the visible light-responsive photocatalyst on the exposed surface, it is possible to suppress the falling off of the visible-light responsive photocatalyst while stably expressing an antiviral function (paragraph 0015). etc).

JP2014-233946A JP2015-212324A JP 2019-60119 Publication Japanese Patent Application Publication No. 11-48412 JP2018-202835A

The present inventors took into consideration the various performances required of plumbing components, and developed a new structure that can further impart antiviral properties to a surface layer that essentially contains (meth)acrylic resin and (meth)acrylic particles. We aimed to realize this. However, we have discovered a novel problem in that even if an inorganic antiviral agent is simply added to the surface layer, sufficient antiviral properties cannot be obtained. It was also confirmed that the anti-slip properties were reduced due to the protrusions on the surface of the surface layer being scraped by sliding. In order to solve these problems, the present inventors segregated an inorganic antiviral agent near the surface of the surface layer, specifically, applied an inorganic antiviral agent on the surface of (meth)acrylic particles It has been found that by segregating in the upper region, it is possible to improve the durability of the surface layer and also to impart good antiviral properties to the surface layer. The present invention is based on this knowledge.

Therefore, an object of the present invention is to provide a plumbing member that has both good antiviral properties and durability.

The plumbing member according to the present invention is
comprising a base material and a surface layer provided on the base material,
The surface layer includes a (meth)acrylic resin, particles, and an inorganic antiviral agent,
The particles are particles made of (meth)acrylic resin,
The inorganic antiviral agent includes an inorganic carrier and an inorganic active ingredient supported on the inorganic carrier,
A region between the outermost surface of the surface layer and a position 2 μm deep from the outermost surface perpendicularly to the substrate direction (hereinafter referred to as “2 μm region”), and within the 2 μm region, The ratio of the volume of the inorganic antiviral agent contained in the target area to the volume of the area above the particle (hereinafter referred to as "target area") in which at least a portion of the particle is contained is 20% or more. That is.

According to the present invention, a plumbing member having both good antiviral properties and durability is provided.

FIG. 1 is a schematic diagram showing an example of a plumbing member according to the present invention. FIG. 2 is a conceptual diagram for explaining a "2 μm region" and a "specific region" in the surface layer included in the plumbing member according to the present invention. 2 is a cross-sectional observation image of the sample of Example 1. 2 is a cross-sectional observation image of a sample of Comparative Example 1.

Water-related member An example of the water-related member according to the present invention will be described with reference to FIG. 1. The plumbing member 1 includes a base material 2 and a surface layer 3 provided on the base material 2. The surface layer 3 includes a (meth)acrylic resin 4, particles 5, and an inorganic antiviral agent 6.

Surface layer The surface layer 3 will be explained below.

Existence state of the inorganic antiviral agent in the surface layer In the present invention, the region between the outermost surface 7 of the surface layer and a position 2 μm deep from the outermost surface 7 perpendicularly to the substrate direction (hereinafter, “2 μm region”) of the inorganic antiviral agent 6 contained in the target area, relative to the volume of the area above the particles 5 (hereinafter referred to as the "target area"), and at least a part of which is contained within the 2 μm area. The volume ratio (hereinafter also referred to as "the volume ratio of the inorganic antiviral agent 6 existing in the region between the particles 5 and the outermost surface 7 of the surface layer 3") is 20% or more. Preferably it is 30% or more. This allows the inorganic antiviral agent 6 to exist at a high volume percentage on or above the surface of the particles 5, that is, in a region near the surface of the surface layer 3. In one embodiment of the present invention, in the surface layer 3, the inorganic antiviral agent 6 is present at a high volume percentage in a region between the particles 5 and the outermost surface 7 of the surface layer so as to cover the particles 5. It is preferable that

Since the volume ratio of the inorganic antiviral agent 6 present in the region between the particles 5 and the outermost surface 7 of the surface layer 3 is 20% or more, the surface layer 3 exhibits good antiviral properties. I can do it. Furthermore, since the inorganic antiviral agent 6 has an active ingredient supported on an inorganic carrier, it has high hardness due to the inorganic carrier. Therefore, since the inorganic antiviral agent 6 having high hardness is present at a high volume percentage on or above the surface of the particles 5, it is also possible to increase the durability of the surface layer 3. As described above, the plumbing member 1 according to the present invention can have both good antiviral properties and durability.

<Method for confirming the presence state of inorganic antiviral agent in the surface layer>
The presence state of the inorganic antiviral agent 6 in the surface layer 3 can be confirmed by analyzing a scanning electron microscope (SEM) image of a cross section of the plumbing member 1. For example, the presence status can be confirmed using the following method.

<Cross-sectional observation>
Cut the plumbing component 1 to an appropriate size, sandwich it with BUEHLER's UniClip, and apply transparent packaging tape (3M Japan) to one side of the holder of Sankei's clear ring for embedding (outer diameter: 1.25 inches). Scotch 315), and place the clip holding the sample in the holder so that it is perpendicular to the area where the tape was pasted. Into the holder in which the sample was placed, a mixed solution of Technovit main agent manufactured by Kemet Japan and Technovit curing agent manufactured by Kemet Japan was mixed at a ratio of 1:2 and poured into the holder. After that, defoaming treatment is performed. Specifically, the sample is placed in a vacuum chamber, the pressure is reduced using a vacuum pump G-50SA made by ULVAC, and the sample is allowed to stand for 5 minutes under an atmosphere of 0.09 MPa. Thereafter, it is allowed to stand for 16 hours in a 30°C environment to be cured. The cured epoxy resin in which the sample was embedded (hereinafter referred to as embedding resin) was taken out from the holder and ground by about 2 mm with #600 abrasive paper using a polisher (Mecatech 250 manufactured by PRESI) to expose the sample from the embedding resin. Thereafter, the sample was buffed with an aqueous solution containing diamond particles (9 μm), then buffed with an aqueous solution containing diamond particles (3 μm), and then buffed with an aqueous solution containing alumina abrasive (φ0.5 μm). Obtain a mirror cross section of.

The obtained mirror cross section was observed with a tabletop scanning electron microscope (JCM-7000 manufactured by JEOL Ltd.), and the interface between the surface layer and the base material was located below the observed image and was horizontal to the observed image. In this state, a backscattered electron image is taken to obtain a cross-sectional observation image. Using the observed image of this cross section, the volume ratio of the inorganic antiviral agent 6 present in the region between the particle 5 and the outermost surface 7 of the surface layer 3 is determined.

<Volume ratio of inorganic antiviral agent present in the region between the particles and the outermost surface of the surface layer>
In the present invention, the volume ratio of the inorganic antiviral agent 6 existing in the region between the particles 5 and the outermost surface 7 of the surface layer 3 will be explained below using the cross-sectional observation image obtained in the above-mentioned cross-sectional observation. Calculated by method. Specifically, it is defined by the area ratio (c') of the inorganic antiviral agent 6 present in the region between the particle 5 and the outermost surface 7 of the surface layer 3. That is, the area ratio of the inorganic antiviral agent 6 existing in the region between the particles 5 and the outermost surface 7 of the surface layer 3 in the cross-sectional observation image is calculated as the area ratio of the particles 5 and the surface layer in the (actual) surface layer 3. This is regarded as the volume ratio of the inorganic antiviral agent 6 existing in the area between the outermost surface 7 of

A method of calculating the area ratio (c') will be explained. First, in the cross-sectional observation image, a region (2 μm region) between the outermost surface 7 of the surface layer 3 and a position at a depth of 2 μm perpendicularly to the substrate direction from the outermost surface 7 is specified. Next, particles that are at least partially contained within the 2 μm region are identified (hereinafter also referred to as “specific particles”). Then, the area (a) of the region (target region) from the surface within the 2 μm region and above the specific particle, that is, the surface included within the 2 μm region of the surface of the specific particle to the outermost surface 7 of the surface layer 3 seek. FIG. 2 shows a conceptual diagram of a 2 μm region and a target region. Furthermore, the area (b) of all the inorganic antiviral agents 6 present in the target area is determined.

Here, in the cross-sectional observation image, the target area is binarized into black and white based on brightness, and the white area is determined to be the area where the inorganic antiviral agent 6 is present. In the cross-sectional observation image, the inorganic antiviral agent 6 appears white compared to the (meth)acrylic resin 4 and particles 5 contained in the surface layer 3. Therefore, the binarization threshold is adjusted so that the inorganic antiviral agent 6 can be visually identified, and the total area of the white area is calculated as the area (b) of the inorganic antiviral agent 6 present in the target area. It can be determined that

The ratio (c) of the area (b) of the inorganic antiviral agent 6 present in the target area to the area (a) of the target area is determined by the following formula (1).
c(%)=b/a×100 Formula (1)

Moreover, the above-mentioned cross-sectional observation is performed in three fields of view for one sample. Calculations are performed using equation (1) for each of the three cross-sectional observation images obtained through observation of these three fields of view, and three (c) values are obtained. These average values (c') are taken as the ratio of the area of the inorganic antiviral agent 6 present in the target area to the area of the target area.

Surface Segregation Rate of Inorganic Antiviral Agent In the present invention, the inorganic antiviral agent 6 is preferably segregated near the surface of the surface layer 3 at a high volume percentage. For example, the total volume of the inorganic antiviral agent 6 contained in the upper half area of the surface layer 3 may be 70% or more of the total volume of the inorganic antiviral agent 6 contained in the entire area of the surface layer 3. More preferably, it is 75% or more, even more preferably. Thereby, the antiviral properties and durability of the surface layer 3 can be further improved.
In the present invention, the ratio of the total volume of the inorganic antiviral agent 6 contained in the upper half area of the surface layer 3 to the total volume of the inorganic antiviral agent 6 contained in the entire area of the surface layer 3 is determined by the above-mentioned cross-sectional observation. It is defined by the surface segregation rate (f) of the inorganic antiviral agent 6 described below, which is calculated using the cross-sectional observation image obtained in . That is, the surface segregation rate (area %) of the inorganic antiviral agent 6 in the cross-sectional observation image is regarded as the surface segregation rate (volume %) of the inorganic antiviral agent 6 in the (actual) surface layer 3 .

<Surface segregation rate (f) of inorganic antiviral agent>
The surface segregation rate (f) of the inorganic antiviral agent 6 is the ratio of the surface layer to the total area (d) of the inorganic antiviral agent 6 contained in the entire surface layer 3 in the cross-sectional observation image obtained in the above-mentioned cross-sectional observation. The ratio of the total area (e) of the inorganic antiviral agent 6 contained on the surface side of 3 is calculated by the following formula (2).
f(%)=e/d×100 Formula (2)

The area (d) of the inorganic antiviral agent 6 contained in the entire surface layer 3 is determined as follows. That is, in the cross-sectional observation image obtained by the above-mentioned cross-sectional observation, the upper end of the surface layer 3 is determined by visual judgment as the outermost surface 7 of the surface layer 3, and the lower end of the surface layer 3 is determined as the outermost surface of the surface layer 3. . In the region sandwiched between the outermost surface 7 of the surface layer 3 and the backmost surface of the surface layer 3, a region corresponding to the inorganic antiviral agent 6 is visually extracted, and the total area of the extracted regions is calculated as the entire surface layer 3. The area (d) of the inorganic antiviral agent 6 contained in

The area (e) of the inorganic antiviral agent 6 contained on the surface side of the surface layer 3 is determined as follows. That is, in the cross-sectional observation image, a perpendicular line is drawn from each point (e.g. each pixel) on the outermost surface 7 of the surface layer 3 to the backmost surface of the surface layer 3, the midpoint of each perpendicular line is extracted, and the middle point of each perpendicular line is extracted. The line connecting the points is defined as the center plane of the surface layer 3. Next, a region sandwiched between the outermost surface 7 of the surface layer 3 and the center plane of the surface layer 3 is defined as a region on the surface side of the surface layer 3. The area on the surface side of the surface layer 3 is binarized into black and white based on the brightness, and the white area is determined to be the area where the inorganic antiviral agent 6 is present and extracted visually. The area of the extracted white region is measured, and the sum is defined as the area (e) of the inorganic antiviral agent 6 contained on the surface side of the surface layer 3.

Components included in the surface layer Each component included in the surface layer 3 will be explained below.

(Meth) acrylic resin (meth) acrylic resin 4 refers to a resin having a (meth) acrylic group or a resin obtained by further polymerizing a (meth) acrylic resin. In the present invention, "(meth)acrylic" means acrylic and methacryl. The (meth)acrylic resin 4 is, for example, polymethyl methacrylate resin, (meth)acrylic ester copolymer, methacrylic ester copolymer, reactive urethane (meth)acrylate oligomer, reactive urethane (meth) It may be an acrylate polymer, a reactive (meth)acrylic polymer, or the like.

The fact that the surface layer contains a (meth)acrylic resin can be confirmed by FT-IR (Fourier transform infrared spectroscopy) and GC-MS (gas chromatography mass spectrometry). Specifically, the surface layer is scraped off, and the scraped surface layer is analyzed by FT-IR. The following are known as typical peaks observed with FT-IR. From these peaks, it can be determined whether (meth)acrylic resin is contained.
2990cm ^-1 : Methyl group C-H Asymmetric stretching 2950cm ^-1 : Methyl group C-H Symmetrical stretching 1725cm ^-1 : Ester group C=O Stretching vibration 1435cm ^-1 : Methylene group C-H Symmetric declination (scissors)
1145 cm ^-1 : Ester group C-O expansion and contraction 750 cm ^-1 : Methylene group C-H Asymmetrical in-plane bending angle (rolling)
Since FT-IR is affected by components contained in the surface layer, it is possible to improve accuracy by analyzing using GC-MS. The mass spectrum obtained by GC-MS is compared and analyzed with a peak library. In this way, it can be determined whether the surface layer contains (meth)acrylic resin.

The amount of (meth)acrylic resin 4 contained in the surface layer 3 is preferably 30% by weight or more and 80% by weight or less. This allows the surface layer to have high durability.

A method for calculating the amount of (meth)acrylic resin 4 contained in the surface layer 3 will be explained. First, a sample containing the surface layer 3 was embedded in an epoxy resin, and a mirror cross section of the resulting surface layer 3 was examined using a scanning electron microscope (for example, JEOL's tabletop scanning electron microscope JCM-7000). ) to obtain an observation image. The observed image of the surface layer 3 is saved as an electronic file in grayscale 24-bit BMP format. The number of pixels of the surface layer 3 in the saved observation image is calculated. Next, the number of pixels of each particle 5 and each inorganic antiviral agent 6 included in the surface layer 3 is calculated. Using these calculated numbers of pixels, the amount (area %) of the (meth)acrylic resin 4 contained in the surface layer 3 is calculated from the following formula.
Amount of (meth)acrylic resin 4 [area %] = (number of pixels of each particle 5 + number of pixels of each inorganic antiviral agent 6) / number of pixels of surface layer 3 x 100

When implementing the above, in the gray scale SEM image, the inorganic antiviral agent 6 appears white compared to the (meth)acrylic resin 4 included in the surface layer 3, so the white part is identified as the inorganic antiviral agent 6. to decide. Furthermore, since the particles 5 appear black compared to the (meth)acrylic resin 4 included in the surface layer 3, the black portions are determined to be the particles 5. Count the number of black pixels (particles 5) and white pixels (inorganic antiviral agent 6).

The particles 5 included in the particle surface layer 3 are particles made of (meth)acrylic resin. Thereby, the adhesion between the (meth)acrylic resin 4 and the particles 5 can be improved. In other words, it is possible to prevent the (meth)acrylic resin 4 or particles 5 from detaching from the surface layer 3. As a result, the durability of the entire surface layer 3 can be improved. Note that the particles 5 may also be referred to as "(meth)acrylic particles 5."

The (meth)acrylic resin constituting the particles 5, like the (meth)acrylic resin 4, refers to a resin having a (meth)acrylic group or a resin obtained by further polymerizing a (meth)acrylic resin. The (meth)acrylic resin constituting the particles 5 is, for example, a polymethyl methacrylate resin, a (meth)acrylic ester copolymer, a (meth)acrylic ester copolymer, or a reactive urethane (meth)acrylate oligomer. , reactive urethane (meth)acrylate polymers, reactive (meth)acrylic polymers, and the like.

The shape of the (meth)acrylic particles 5 may be spherical, ellipsoidal, geometric, rod-like, fibrous, or irregular. Among these, spherical shapes are preferred. Thereby, the surface shape of the surface layer can be made rounded. Therefore, it is possible to suppress objects from getting caught on the surface of the surface layer, for example, when brushes, sponges, cloths, etc. are slid during cleaning. As a result, the durability of the surface layer can be improved.

The volume average particle diameter of the (meth)acrylic particles 5 is preferably larger than the volume average particle diameter of the inorganic carrier contained in the inorganic antiviral agent 6 described below. This makes it easier for the inorganic antiviral agent 6 to exist on or above the surface of the (meth)acrylic particles 5 in the surface layer 3, making it possible for the surface layer 3 to have both antiviral properties and durability. .
Further, the average volume particle diameter of the (meth)acrylic particles 5 is more preferably twice or more the average volume particle diameter of the inorganic carrier contained in the inorganic antiviral agent 6. Thereby, the inorganic antiviral agent 6 is more likely to exist on or above the surface of the (meth)acrylic particles 5, and the antiviral properties and durability of the surface layer 3 can be further improved.

The volume average particle diameter of the (meth)acrylic particles 5 is preferably larger than the thickness of the surface layer 3, which will be described later. Thereby, it becomes possible to obtain the anti-slip property and the design required for the plumbing member 1.

The amount of (meth)acrylic particles 5 contained in the surface layer 3 is preferably 10% by weight or more and 20% by weight or less. Thereby, the surface layer 3 can ensure good anti-slip properties and design (for example, a design with a uniform matte feel) while exhibiting durability.

The inorganic antiviral agent 6 contained in the inorganic antiviral agent surface layer 3 includes an inorganic carrier and an inorganic active ingredient supported on the inorganic carrier. Such an inorganic antiviral agent 6 is less irritating to the skin than an organic antiviral agent, and is therefore preferable for a plumbing member having a surface layer that is touched by a person.

Inorganic carriers include zeolite, (calcium) apatite, zirconia, zirconium phosphate, calcium phosphate, calcium zinc phosphate, silica gel, calcium silicate, magnesium aluminate silicate, titanium oxide, potassium titanate, silica, alumina, Meltable glass, thiosulfite, etc. can be used.

As the inorganic active ingredient, metal ions can be used, such as silver ions, copper (I) ions, copper (II) ions, zinc ions, gold ions, cobalt ions, nickel ions, palladium ions, iron (III) ions, etc. ) ions, aluminum (III) ions, zirconium (II) ions, manganese (II) ions, barium (II) ions, calcium (II) ions, and sodium ions can be used. Among these, silver ions, copper (I) ions, copper (II) ions, and zinc ions are preferred, and silver ions are more preferred. Silver ions can exhibit antiviral properties in small amounts compared to other metal ions.

The volume average particle diameter of the inorganic carrier contained in the inorganic antiviral agent 6 is preferably smaller than the volume average particle diameter of the (meth)acrylic particles 5. This facilitates the presence of the inorganic antiviral agent 6 on or above the (meth)acrylic particles 5 in the surface layer 3, making it possible for the surface layer 3 to have both antiviral properties and durability.
Further, the average volume particle diameter of the inorganic carrier contained in the inorganic antiviral agent 6 is more preferably half or less of the average volume particle diameter of the (meth)acrylic particles 5. Thereby, the inorganic antiviral agent 6 is more likely to exist on or above the (meth)acrylic particles 5, and the antiviral properties and durability of the surface layer 3 can be further improved.

The amount of inorganic antiviral agent 6 contained in the entire surface layer 3 is more preferably 0.3% by weight or more and 4% by weight or less. Thereby, the inorganic antiviral agent 6 can easily exist on or above the surface layer 3 at a desired volume ratio while exhibiting good antiviral properties. As a result, the surface layer 3 can have both antiviral properties and durability. Furthermore, discoloration of the surface layer 3 can be suppressed.

It is preferable that the amount of the active ingredient supported on the inorganic carrier is, for example, 0.2% by mass or more.

Other components Sulfonic acid group or sulfonic acid group In the present invention, the surface layer preferably contains a sulfonic acid group or sulfonic acid group at least on the surface. This makes it possible to impart hydrophilicity to the surface layer. As a result, drainage and drying properties are improved, and it is possible to suppress the adhesion of stains such as limescale due to residual water, and it is also possible to suppress the adhesion of oil. According to a preferred embodiment of the invention, the surface layer contains sulfonic acid groups or sulfonic acid groups on its surface. According to a more preferred embodiment of the invention, the surface layer contains more sulfonic acid groups or sulfonic acid groups on its surface than in its interior. That is, it is more preferable that sulfonic acid groups or sulfonic acid groups are segregated on the surface of the surface layer. Compounds that provide sulfonic acid groups or sulfonic acid groups to the surface layer will be described later.

Surface Properties of Surface Layer In the present invention, since the surface layer 3 has the above-described configuration, it can have the following surface properties.

<Hardness>
In the present invention, the hardness of the surface layer can be expressed using pencil hardness as an index. The pencil hardness of the surface layer is preferably 1H or higher, more preferably 5H or higher. This makes it possible to increase the durability of the surface layer. Therefore, even if cleaning by sliding or the like is repeated, damage to the surface of the surface layer can be prevented.
The pencil hardness of the surface layer can be measured according to scratch hardness (pencil method) JIS K 5600-5-4.

<Surface roughness>
In the present invention, the surface roughness (Ra) of the surface layer is preferably 0.1 or more, more preferably 2.0 or more. This provides a highly anti-slip surface. In addition, since the surface of the surface layer is uneven, it becomes easier to apply a load during sliding, but in the present invention, the inorganic antiviral agent 6 is present on or above the surface of the (meth)acrylic particles 5. Therefore, good durability that can withstand the load can also be obtained.

As the surface roughness (Ra) of the surface layer, for example, the value of the arithmetic mean roughness (Ra) of the surface layer is measured using a stylus type surface roughness measuring machine (manufactured by Tokyo Seimitsu Co., Ltd., SURFCOM 15OODX). be able to. The measurement conditions can be as follows.
(Measurement condition)
Measurement type: Roughness measurement Measurement length: 10mm
Cutoff wavelength: 0.25mm
Measurement range: ±128.0μm
Speed: 0.3mm/s
Cutoff type: Gaussian

<Slip resistance when wet>
Since the surface layer has the above-described structure, it has good anti-slip properties. For example, the anti-slip properties of the surface layer 3 can be evaluated using the anti-slip properties of the surface layer when wet as an index. For example, the anti-slip property when wet can be evaluated by dropping 2 mL of ion-exchanged water onto the surface of the surface layer using a dropper and pressing the palm of the hand against the surface of the surface layer.

<Design>
Since the surface layer has the above-described structure, it has good design properties. For example, it is possible to ensure a uniform and matte design. Designability can be evaluated, for example, by measuring glossiness. Specifically, the evaluation can be made by measuring the glossiness of the surface layer at 60° using a glossmeter (Nippon Denshoku Industries Co., Ltd. VG7000). Further, the appearance of the surface layer (matteness, presence or absence of shine, etc.) may be visually evaluated.

Thickness of Surface Layer The thickness of the surface layer 3 may be determined as appropriate depending on the use of the plumbing member 1. In the present invention, the thickness of the surface layer 3 is preferably 5 μm or more and 20 μm or less. When the film thickness is 20 μm or less, sedimentation of the inorganic antiviral agent 6 during the production of the surface layer can be suppressed, and the inorganic antiviral agent 6 can be easily present near the surface of the surface layer. When the film thickness is 5 μm or more, it becomes easier to form a uniform film.

<Method for measuring surface layer thickness>
The thickness t of the surface layer 3 can be calculated from the weight of the surface layer. First, the initial weight of the base material is measured. Next, the weight of the water-related member after the surface layer 3 is formed on the base material is measured. The weight of the surface layer 3 is obtained by subtracting the weight of the base material from the weight of the water-related member. Here, assuming that the surface layer 3 is uniformly formed on the base material, the thickness (t) of the surface layer 3 is calculated from the following formula.
Thickness t (μm) of surface layer 3 = Weight (g) of surface layer 3 ÷ Area of surface of base material (cm ² ) ÷ Density of surface layer 3 (g/cm ³ )×10 ⁴

The thickness t of the surface layer can also be determined by a method other than the above measurement method. Examples include a method of observing and measuring the cross section of the plumbing member 1 with a microscope, a method of measuring with a reflectance film thickness meter, and the like.
Examples of methods for observing and measuring the cross section of the plumbing member 1 using a microscope include the following method.
The surface layer 3 is specified in the cross section of the plumbing member 1 to be evaluated. For example, the boundary line between the surface layer 3 and a layer other than the surface layer (base material 2 or intermediate layer) is adjusted by polishing or the like until it becomes distinguishable. The thickness of the surface layer 3 can be measured by observing the cross section obtained by polishing using a microscopic observation means. If the outermost surface 7 of the surface layer and the interface between the surface layer 3 and, for example, the base material 2 have poor linearity and it is difficult to determine the distance between the interfaces, The film thickness of the surface layer 3 may be measured by dividing the area of the cross section of the surface layer 3 included in the observed image by the length of a straight line that approximates the interface between the two. In addition, in order to determine and use the length of the interface between the surface layer 3 and the base material side, when obtaining an observation image by microscopic observation, the interface between the surface layer 3 and the base material 2, and a straight line approximating the interface, are The observation image may be photographed in a horizontal state within the observation image.
The microscopic observation means used for observation include, for example, optical microscope, digital microscope, SEM (scanning electron microscope), TEM (transmission electron microscope), mapping by EDS/EDX (energy dispersive X-ray spectroscopy), etc. can be mentioned. In particular, observation using a backscattered electron image using an SEM can be suitably used for the above observation because it is easy to detect material differences inside the surface layer 3 with high resolution.

In the present invention, it is preferable that the (meth)acrylic particles 5 are buried in the surface layer 3. This makes it possible to obtain durability while ensuring the anti-slip properties and design of the surface layer.

Composition for forming surface layer The composition for forming surface layer 3 will be explained. The composition preferably contains a film-forming component, particles 5, and an inorganic antiviral agent 6. The film-forming component is a (meth)acrylic monomer, oligomer, or polymer that is cured to become the (meth)acrylic resin 4. The particles 5 and the inorganic antiviral agent 6 are as described above.
<Film-forming components>
In the present invention, it is preferable to use a polyfunctional (meth)acrylic monomer, oligomer, or polymer having three or more functional groups in one molecule as the film-forming component. Thereby, the cured product of the composition (that is, "surface layer 3") can be made into a three-dimensional highly crosslinked coating film. Thereby, the surface layer 3 can have good durability. It is more preferable that the polyfunctional (meth)acrylic monomer, oligomer or polymer has five or more functional groups. Thereby, the coating film becomes more highly crosslinked, and the durability of the surface layer 3 can be improved.

In the present invention, the film-forming component preferably contains 10% by weight or more, more preferably 20% by weight or more of a polyfunctional (meth)acrylic monomer, oligomer, or polymer having three or more functional groups in one molecule. . Thereby, the durability of the surface layer can be improved.

In the present invention, the functional group is preferably an ethylenically unsaturated group. Ethylenically unsaturated groups have good reactivity and can increase the hardness of the surface layer. The ethylenically unsaturated group is preferably a vinyl group, an acryloyl group, or a methacryloyl group, more preferably an acryloyl group or a methacryloyl group.

Examples of (meth)acrylic monomers (oligomers) having three or more functional groups include ethoxylated isocyanuric acid triacrylate, ε-caprolactone modified tris-(2-acryloxyethyl) isocyanurate, pentaerythritol triacrylate, and trimethylol. Propane triacrylate, ditrimethylolpropane trimethacrylate, ethoxylated glycerin triacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, trimethylolpropane triacrylate Examples include acrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polytetramethylene glycol diacrylate, glycerin triacrylate ethoxylate, dipentaerythritol polyacrylate, and the like.

<Solvent>
In the present invention, the composition may contain a solvent in order to improve wettability to the substrate and adjust the viscosity of the composition. For example, it is preferable that the composition contains about 60% by weight of the solvent. Examples of such solvents include alcohols such as methanol, ethanol, IPA (isopropanol), and n-butanol, and cellosolves such as methoxyethanol and methoxypropanol, from the viewpoint of compatibility with other compounds contained in the composition. Examples include acetone, ketones such as MEK (methyl ethyl ketone), ethyl acetate, butyl acetate, THF (tetrahydrofuran), toluene, PEGMEA (propylene glycol monomethyl ether acetate), DMF (N,N'-dimethylformamide) and water. However, it is not limited to these. A plurality of types of solvents may be mixed and used as necessary.

<Polymerization initiator>
In the present invention, as described below, the composition preferably contains a polymerization initiator in order to cure (polymerize) the uncured film of the composition.
When the uncured film of the composition is cured (polymerized) by heat, the composition may contain a known radical polymerization initiator, curing catalyst, polymerization accelerator, and the like. As a thermal polymerization initiator, for example, azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, benzoyl peroxide. etc. may be used.
When the uncured film of the composition is cured (polymerized) by radiation, for example, active energy rays such as ultraviolet rays and visible light, the composition may contain a known photopolymerization initiator. For example, benzophenone, (±)-camphorquinone, acetophenone, 4'-hydroxyacetophenone, 3-methylbenzophenone, 1,4-dibenzoylbenzene, 1-benzoylcyclohexanol, 2-chlorothioxanthone, and the like may be used. As the photopolymerization initiator, a mixture of 1-hydroxycyclohexylphenyl ketone and benzophenone in a weight ratio of 1:1 is preferred.

<Curing catalyst>
In the present invention, the composition may include a curing catalyst. For example, dinonylnaphthalene disulfonic acid catalyst, dinonylnaphthalene (mono)sulfonic acid catalyst, dodecylbenzenesulfonic acid catalyst, dodecylbenzenesulfonic acid catalyst (block acid catalyst), p-toluenesulfonic acid catalyst (block acid catalyst), phosphoric acid catalyst Catalysts, phosphoric acid block catalysts, tin catalysts, etc.

<Other ingredients>
Sulfonic acid group or compound having a sulfonic acid group In the present invention, the composition is a compound that provides a sulfonic acid group or a sulfonic acid group to the surface layer, for example, a sulfonic acid group or a compound having at least one sulfonic acid group in the molecule. and ethylenically unsaturated groups. Specific examples include sodium or potassium salts of 2-((meth)acryloyloxy)ethanesulfonic acid, 3-((meth)acryloyloxy)propane-1-sulfonic acid, and acrylamide tert-butylsulfonic acid. Preferably, linear alkylsulfonic acids having a (meth)acryloyloxy group and their salts, 2-((meth)acryloyloxy)ethanesulfonic acid, potassium 3-((meth)acryloyloxy)propane-1-sulfonate. (3-sulfopropyl potassium methacrylate). In addition, examples of compounds having a sulfonic acid group or a sulfonic acid group and at least one ethylenically unsaturated group in the molecule include methacryl sulfonic acid, sodium or potassium salt of p-styrene sulfonic acid, alkylsulfosuccinic acid alkenyl ether salt, Oxyethylene (meth)acrylate sulfate salt, alkylsulfosuccinic acid alkenyl ester salt, glycerol-1-allyl-3-alkylphenyl-2-polyoxyethylene sulfate, etc. can also be used.

Volatile Compound In the present invention, the composition is a compound that can segregate a sulfonic acid group or sulfonic acid group on the surface of the surface layer, for example, a compound that has a molecular weight lower than that of the compound containing the sulfonic acid group or sulfonic acid group. It can include small, volatile compounds with one ethylenically unsaturated group and a hydrophilic group in the molecule. Specifically, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate and its structural isomers, hydroxybutyl (meth)acrylate and its structural isomers, and tetrahydrofurfuryl (meth)acrylate. , (meth)acryloylmorpholine, N-vinylformamide, (meth)acrylic acid, and the like. Among these, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, and (meth)acrylic acid are preferred from the viewpoint of compatibility with a sulfonic acid group or a compound containing a sulfonic acid group.

Pigment In the present invention, the composition may contain a pigment. For example, zinc white, lead white, litobone, titanium dioxide, precipitated barium sulfate and pallite powder, red lead, iron oxide red, yellow lead, zinc yellow (zinc yellow 1 type, zinc yellow 2 types), ultramarine blue, Prussia. It may contain blue (ferropotassium ferrocyanide), carbon black, etc.

Ultraviolet Absorber In the present invention, the composition may contain an ultraviolet absorber. For example, it contains ethylhexyl methoxycinnamate, octyl methoxycinnamate, ethylhexyl para-methoxycinnamate, hexyl diethylaminohydroxybenzoylbenzoate, bisethylhexyloxyphenol methoxyphenyltriazine, t-butylmethoxydibenzoylmethane, octyltriazone, octocrylene, etc. Good too.

Method for Preparing Surface Layer In the present invention, the method for preparing the surface layer 3 is particularly limited as long as it is a method that can segregate the inorganic antiviral agent 6 near the surface of the surface layer 3 at a high volume ratio. Not done. For example, it can be produced by the following method.

<Preparation of base material>
First, the base material 2 is prepared. If necessary, the substrate surface is pretreated. For example, an intermediate layer may be formed on the surface of the base material.

<Coating process>
Next, a composition for forming a surface layer is applied onto the base material 2. As the composition, it is possible to use, for example, a composition containing a film-forming component, particles 5, and inorganic antiviral agent 6 as described above. Alternatively, it is also possible to prepare two types of compositions and apply them respectively. In this case, composition C1 containing no inorganic antiviral agent is first applied to form a (wet) coating of composition C1. Thereafter, composition C2 containing an inorganic antiviral agent is applied onto the (wet) coating of composition C1 to form a (wet) coating of composition C2.
According to one aspect of the present invention, the composition C1 applied for the first time contains only the film-forming component and (meth)acrylic particles 5, which will be described later, and the composition C2 applied for the second time contains only the film-forming component and (meth)acrylic particles 5. It is preferable that only the inorganic antiviral agent 6 is included.
According to another aspect of the present invention, two or more (meth)acrylic particles 5 having different volume average particle diameters are prepared, two or more compositions containing each of them are prepared, and the particles having a large volume average particle diameter are prepared. The composition containing the (meth)acrylic particles 5 is applied two or more times in order, the (meth)acrylic particles 5 are arranged so as to physically suppress the sedimentation of the inorganic antiviral agent 6, and then the inorganic antiviral agent 6 is applied. A composition containing Agent 6 may be applied. This makes it more reliable to segregate the inorganic antiviral agent 6 near the surface of the surface layer 3 at a high volume ratio.
In the present invention, known methods such as brush coating, spray coating, dip coating, spin coating, and curtain coating can be used as a method for applying the composition to the substrate.

<Drying process>
Then, a (wet) application of the composition formed on the substrate 2 (in the case of application of two compositions, a (wet) application of composition C1 and a (wet) application of composition C2). is dried to obtain an uncured film. At this time, it is sufficient that the (wet) coated material can be dried, and if necessary, it may be dried by heating. By drying (heating), the solvent and optionally volatile compounds contained in the (wet) coating are evaporated.

As the heat drying method, a known method of drying with infrared rays, hot air, etc. can be used. The heating temperature is usually room temperature to 200°C, preferably 35°C to 150°C, more preferably 40°C to 100°C. The drying time may be determined as appropriate within a range that allows sufficient volatilization of the solvent.

<Curing process>
Next, the uncured film is cured. That is, a film-forming component (as the case may be, a sulfonic acid group or a compound containing a sulfonic acid group) is copolymerized. As a curing method, known methods such as thermosetting, active energy ray curing, or a combination thereof can be used.

When performing polymerization curing by thermosetting, the above-mentioned polymerization initiator can be used. Further, as a heating method, a known method of heating with infrared rays, hot air, etc. can be used, similar to the drying step of the (wet) coated material described above. In the case of thermal curing, the drying step and curing step of the (wet) coated material can be performed simultaneously in one step.

When performing polymerization curing with active energy rays, examples of the radiation include visible light of 400 to 800 nm, ultraviolet rays of 400 nm or less, or electron beams, but ultraviolet rays are preferable because they can carry out polymerization easily and in a short time. preferable. When curing is performed using ultraviolet rays, a known photopolymerization initiator is used. Examples of sources of ultraviolet light include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, ultraviolet lasers, deep ultraviolet LED lamps, and ultraviolet rays from sunlight. The irradiation atmosphere may be in the air or under an inert gas such as nitrogen or argon.

Performance of plumbing parts
Antiviral properties The plumbing member according to the present invention has good antiviral properties as described above. In the present invention, the antiviral property of the plumbing member 1 (i.e., the surface layer 3) is preferably such that the antiviral activity value determined by the following test method in accordance with JIS R1756 (2020) in the dark is 2 or more.
<Antiviral evaluation method>
The antiviral properties of the plumbing member 1 are evaluated according to JIS R1756 (2020) in the dark. Specifically, an antiviral test is performed using bacteriophage Qβ, and the antiviral activity value (V) in the dark is calculated using the following formula.
Antiviral activity value: V=Log ₁₀ (UV/TV)
TV: Bacteriophage infectivity titer (pfu) 24 hours after dropping bacteriophage liquid
UV: bacteriophage infectivity value (pfu) immediately after dropping bacteriophage liquid

Durability The plumbing member according to the present invention has high durability as described above. In the present invention, durability refers to the ability to sufficiently withstand the load applied when sliding the surface of the surface layer 3 using a brush, sponge, cloth, etc. during cleaning, for example. The durability of the surface layer can be evaluated, for example, as follows.
Fix the sample of water-related parts to an abrasion and friction tester (AB-504 Washability Tester, Tester Sangyo Co., Ltd.). Next, drop an appropriate amount of detergent into the center of the sample. Fix a brush etc. to the test machine, place a weight on the brush, and slide the brush over the sample. Subsequently, the surface of the sample is observed by SEM, and the wear state can be evaluated based on the degree of chipping of the (meth)acrylic particles 5, for example.

Applications of Plumbing Parts The plumbing parts according to the present invention are used, for example, in toilets, bathrooms, kitchens, vanities, and the like. Specifically, our products include bathroom wall materials, bathroom floor materials, bathroom counters, bathtubs, bathtub rims, bathroom window materials, bathroom door materials, shower booth wall materials, washbasin mirrors, washstands, washbowls, kitchen counters, Uses include, but are not limited to, kitchen doors, storage shelves, storage boards, toilet bowls, toilet seats, warm water washing toilet seats and their cleaning nozzles, drains, faucet fittings, range hood materials, etc.

Base material of water-related member In the present invention, the base material 2 of the water-related member 1 is not particularly limited. Examples of the material for the base material 2 include metal, glass, resin, paper, and wood materials. Among these, resin materials are preferred. Examples of resin materials include thermosetting resins and thermoplastic resins. As the thermosetting resin, it is possible to use one or more selected from urea resin, melamine resin, phenol resin, unsaturated polyester resin, epoxy resin, and silicone resin. Thermoplastic resins include polypropylene resin (PP), polyethylene resin (PE), polyacetal resin (POM), polybutylene terephthalate resin (PBT), polyvinyl chloride resin (PVC), polystyrene resin (PS), acrylonitrile-butadiene-styrene. Copolymer resin (ABS), polyphenylene sulfide resin (PPS), polyethylene terephthalate resin (PET), polymethyl methacrylate resin (PMMA), polyamide resin (PA), polyether ether ketone resin (PEEK), polytrimethylene terephthalate resin (PTT), polycarbonate resin (PC), and polytetrafluoroethylene (PTFE) (tetrafluoroethylene resin). In the present invention, it is preferable to use a thermoplastic resin as the resin. More preferably, the resin is one or more selected from PP, PE, POM, PBT, PVC, ABS, PPS, PET, PMMA, PA, and PC. Even more preferred among these are one or more selected from PP, POM, PBT, ABS, and PMMA. In the present invention, since the surface layer 3 contains the (meth)acrylic resin 4, the base material 2 made of acrylic resin material has good affinity (for example, adhesion) with the surface layer 3. Further, the shape of the base material 2 is not particularly limited, and examples include a planar shape and a three-dimensional shape.

In the present invention, the surface layer 3 may be directly formed on the surface of the base material 2, or another layer may be formed between the base material 2 and the surface layer 3. For example, an intermediate layer may be formed between the base material 2 and the surface layer 3 to improve adhesiveness.

The present invention will be specifically explained based on the following examples, but the present invention is not limited to these examples.

1. Preparation <particles>
The following three types of particles were prepared.
・Organic particles 1: (meth)acrylic particles with a volume average particle diameter of 6 μm ・Organic particles 2: (meth)acrylic particles with a volume average particle diameter of 19 μm ・Organic particles 3: (meth)acrylic particles with a volume average particle diameter of 35 μm particle

<Inorganic antiviral agent>
An inorganic antiviral agent was prepared in which 0.2% by mass of silver ions were supported on zirconium phosphate (volume average particle diameter: 1.5 μm) as an inorganic carrier.

<Base material>
An acrylic plate (size: 100 mm x 100 mm x 2 mm, Acrylite EX (registered trademark) manufactured by Mitsubishi Chemical) containing PMMA as a main component was prepared (substrate S).

<Paint>
26.5 g of dipentaerythritol hexaacrylate and 11.5 g of an acrylic oligomer having three or more ethylene groups as film-forming components, and 1-hydroxycyclohexylphenyl ketone and benzophenone as photopolymerization initiators in a weight ratio of 1:1. A solution containing 0.6 g of the mixture and 44 g of 2-methoxyethanol as a solvent was stirred with a stirrer for 60 minutes to prepare paint 1.

2. Preparation of Compositions Coating 1 and a solution obtained by mixing each material shown in Table 1 below in the amounts shown in the same table were mixed and stirred for 60 minutes with a stirrer to prepare Compositions 1 to 10. The amount of each material shown in Table 1 is the amount (wt%) when the amount of paint 1 is 100% by weight.

3. Preparation of sample of plumbing parts
Example 1
Composition 2 was applied onto the substrate S by spray painting using a spray gun (Meiji Kikai Seisakusho Finer II) so that the thickness of the coating film was approximately 8 to 12 μm. Subsequently, Composition 1 was applied using a spray gun (Meiji Kikai Seisakusho Finer II) so that the thickness of the coating film was approximately 3 μm. Thereafter, the mixture was dried by heating at 60° C. for 6 minutes in an air blower constant temperature incubator (DKN402 manufactured by Yamato Scientific Co., Ltd.) to evaporate the solvent. Thereafter, the sample of Example 1 was taken out of the air blower constant temperature incubator and cured by irradiating ultraviolet rays with an ultraviolet curing device (ANUP4154 manufactured by Panasonic Electric Works) equipped with a high-pressure mercury lamp so that the cumulative light amount was 1000 mJ/ ^cm2 . was created.

Example 2
A sample of Example 2 was prepared in the same manner as Example 1 except that Composition 3 was used instead of Composition 2.

Example 3
Composition 4 was applied onto the substrate S by spray painting using a spray gun (Meiji Kikai Seisakusho Finer II) so that the thickness of the coating film was approximately 4 to 5 μm. Subsequently, Composition 1 was applied using a spray gun (Meiji Kikai Seisakusho Finer II) so that the thickness of the coating film was approximately 1 to 2 μm. Thereafter, in the same manner as in Example 1, a sample of Example 3 was produced.

Example 4
A sample of Example 4 was prepared in the same manner as Example 1 except that Composition 5 was used instead of Composition 2.

Comparative example 1
Composition 6 was applied onto the substrate S by spray painting using a spray gun (Meiji Kikai Seisakusho Finer II) so that the thickness of the coating film was approximately 11 to 15 μm. Thereafter, it was heated and dried for 6 minutes in a 60° C. blower constant temperature incubator (Yamato Scientific Co., Ltd. DKN402). Thereafter, in an ultraviolet curing device (Panasonic Electric Works ANUP4154) equipped with a high-pressure mercury lamp, ultraviolet rays were irradiated and cured at an integrated light amount of 1000 mJ/cm ² to prepare a sample of Comparative Example 1.

Comparative example 2
Composition 8 was applied onto the substrate S by spray painting using a spray gun (Meiji Kikai Seisakusho Finer II) so that the thickness of the coating film was approximately 8 to 12 μm. Subsequently, Composition 7 was applied using a spray gun (Meiji Kikai Seisakusho Finer II) so that the thickness of the coating film was approximately 3 μm. Thereafter, it was heated and dried for 6 minutes in a 60° C. blower constant temperature incubator (Yamato Scientific Co., Ltd. DKN402). Thereafter, the coating film was cured by irradiating ultraviolet rays with an ultraviolet curing device (Panasonic Electric Works ANUP4154) equipped with a high-pressure mercury lamp so that the cumulative amount of light was 1000 mJ/cm ² to prepare a sample of Comparative Example 2.

Comparative example 3
A sample of Comparative Example 3 was prepared in the same manner as Comparative Example 1 except that Composition 9 was used instead of Composition 6.

Comparative example 4
Composition 10 was applied onto the substrate S by spray painting using a spray gun (Meiji Kikai Seisakusho Finer II) so that the thickness of the coating film was approximately 11 to 15 μm. Thereafter, it was heated and dried for 6 minutes in a 60° C. blower constant temperature incubator (Yamato Scientific Co., Ltd. DKN402). Thereafter, in an ultraviolet curing device (Panasonic Electric Works ANUP4154) equipped with a high-pressure mercury lamp, ultraviolet rays were irradiated and cured so that the cumulative light amount was 1000 mJ/cm ² to prepare a sample of Comparative Example 4.

4. Evaluation Each sample prepared was evaluated as follows.

(1) Surface layer coating film hardness test The pencil hardness of each sample was measured according to scratch hardness (pencil method) JIS K 5600-5-4. The results are listed in Table 2.

(2) Cross-sectional observation Cut each sample into a size of 5 mm x 7 mm x 2 mm, sandwich it with BUEHLER's UniClip, and place it on one side of the holder of Sankei's clear ring for embedding (outer diameter: 1.25 inches). Transparent packaging tape (Scotch 315, manufactured by 3M Japan) was attached, and a clip holding the sample was placed vertically in the part of the holder where the tape was attached. Into the holder in which the sample was placed, a mixed solution of Technovit main agent manufactured by Kemet Japan and Technovit curing agent manufactured by Kemet Japan in a ratio of 1:2 was poured. After that, defoaming treatment was performed. Specifically, it was placed in a vacuum chamber, the pressure was reduced using a vacuum pump G-50SA manufactured by ULVAC, and the sample was left standing for 5 minutes under an atmosphere of 0.09 MPa. Thereafter, it was allowed to stand for 16 hours in a 30°C environment to be cured. The cured epoxy resin in which the sample was embedded (hereinafter referred to as embedding resin) was taken out from the holder, and was ground by approximately 2 mm with #600 abrasive paper using a polisher (Mecatech 250 manufactured by PRESI) to expose the sample from the embedding resin. . Thereafter, the sample was buffed with an aqueous solution containing diamond particles (9 μm), then buffed with an aqueous solution containing diamond particles (3 μm), and then buffed with an aqueous solution containing alumina abrasive (φ0.5 μm). A mirror cross section was obtained.

The obtained mirror cross section was observed with a tabletop scanning electron microscope (JCM-7000 manufactured by JEOL Ltd.), and the interface between the surface layer and the base material was located below the observed image and was horizontal to the observed image. In this state, a backscattered electron image was taken to obtain a cross-sectional observation image. The observed image of the cross section was saved as an electronic file using the 24-bit grayscale BMP method and used for measurements and calculations in (3) to (5) described below. As representative examples, cross-sectional images of samples of Example 1 and Comparative Example 1 are shown in FIGS. 3 and 4.

(3) Amount of particles contained in the surface layer (volume %)
The amount of particles contained in the surface layer (c) is the ratio of the particle portion contained in the cross section of the surface layer to the cross-sectional area (a) of the surface layer in the cross-sectional observation image obtained in "(2) Cross-sectional observation" above. The ratio of area (b) was calculated using the following formula (1).
c [volume%]=b/a×100 Formula (1)

The cross-sectional area (a) of the surface layer and the area (b) of the particle portion included in the cross-section of the surface layer were analyzed using image processing software (WinROOF2017, manufactured by Mitani Shoji Co., Ltd.) and derived by the following method.
First, the outer circumference of the surface layer in the cross-sectional observation image was determined visually, and the outer circumference was manually drawn using the measurement mode "polygon". Thereafter, the portion surrounded by the outer periphery was extracted as a cross section of the surface layer, and the area of the extracted region was defined as the cross-sectional area (a) of the surface layer.
Next, the particle portion in the cross-sectional observation image was visually determined and extracted manually using a three-point designation circle. The sum of the areas of the extracted three-point designation circles was defined as the area (b) of the particle portion included in the cross section of the surface layer.
Furthermore, the above-mentioned "(2) cross-sectional observation" was performed in three fields of view for one sample. For each of the three cross-sectional observation images obtained in these three visual field observations, calculations were performed using equation (1) to obtain three (c) values. These average values were taken as the abundance (c') of particles contained in the surface layer of the sample.
The results are listed in Table 2.

(4) Surface segregation rate of inorganic antiviral agent The surface segregation rate (f) of an inorganic antiviral agent is the amount of inorganic material contained in the entire surface layer in the cross-sectional observation image obtained in "(2) Cross-sectional observation" above. The ratio of the total area (e) of the inorganic antiviral agent contained on the surface side of the surface layer to the total area (d) of the antiviral agent was calculated using the following formula (2).
f [volume%]=e/d×100 Formula (2)

The area (d) of the inorganic antiviral agent contained in the entire surface layer was determined as follows. That is, in the cross-sectional observation image obtained in "(2) Cross-sectional observation" above, the upper end of the surface layer is determined by visual judgment to be the outermost surface of the surface layer, and the surface layer corresponding to the interface between the surface layer and the base material is determined by visual judgment. The lower end of was the backmost layer of the surface layer. In the area sandwiched between the outermost surface of the surface layer and the backmost surface layer, the area corresponding to the inorganic antiviral agent is visually extracted, and the total area of the extracted area is calculated as the area corresponding to the inorganic antiviral agent contained in the entire surface layer. It was defined as the area (d) of the antiviral agent.

The area (e) of the inorganic antiviral agent contained on the surface side of the surface layer was determined as follows. That is, in the cross-sectional observation image, a perpendicular line is drawn from each point (e.g. each pixel) on the outermost surface of the surface layer to the backmost surface of the surface layer, the midpoint of each perpendicular line is extracted, and these midpoints are connected. The line was taken as the center plane of the surface layer. Next, a region sandwiched between the outermost surface of the surface layer and the center plane of the surface layer was defined as a region on the surface side of the surface layer. The area on the surface side of this surface layer was binarized into black and white based on the brightness, and the white area was determined to be the area where the inorganic antiviral agent was present, and was visually extracted. The area of the extracted white region was measured, and the sum total was taken as the area (e) of the inorganic antiviral agent contained on the surface side of the surface layer.
The results are listed in Table 2.

(5) Area ratio of inorganic antiviral agent present in the region between the particle and the outermost surface of the surface layer The method described below using the cross-sectional observation image obtained in "(2) Cross-sectional observation" above Then, the area ratio (c') of the inorganic antiviral agent 6 existing in the region between the particle 5 and the outermost surface 7 of the surface layer was determined.
A method for calculating the area ratio (c') will be explained. First, in the cross-sectional observation image, a region (2 μm region) between the outermost surface of the surface layer and a position 2 μm deep from the outermost surface in the rearmost direction was identified. Next, particles at least partially contained within the 2 μm region were identified (specific particles). Then, find the area (a) of the region (target region) within the 2 μm region and above the specific particle, that is, from the surface included within the 2 μm region of the surface of the specific particle to the outermost surface of the surface layer. Ta. Furthermore, the area (b) of the inorganic antiviral agent contained in the target region was determined. The target area was binarized into black and white based on brightness, and the white area was determined to be the area where the inorganic antiviral agent was present. The ratio (c) of the area (b) of the inorganic antiviral agent present in the target region to the area (a) of the target region was determined using the following formula (1).
c(%)=b/a×100 Formula (1)

Furthermore, the above-mentioned "(2) cross-sectional observation" was performed in three fields of view for one sample. For each of the three cross-sectional observation images obtained in these three visual field observations, calculations were performed using equation (1) to obtain three (c) values. These average values (c') were taken as the ratio of the area of the inorganic antiviral agent present in the target area to the area of the target area.
The area ratio (c') was regarded as the volume ratio of the inorganic antiviral agent 6 present in the region between the particles 5 and the outermost surface 7 of the surface layer 3 in the surface layer 3. The results are listed in Table 2.

(6) Evaluation of durability Each sample was cut into a size of 100 mm x 40 mm x 2 mm and fixed in an abrasion friction tester (AB-504 washability tester manufactured by Tester Sangyo Co., Ltd.). Subsequently, about 20 to 30 mL of Look Bath Shining Wash (LION Co., Ltd.) was directly dropped into the center of the cut sample. A nylon floor brush (TOTO Corporation EKL00034) was cut into 25 mm pieces and fixed to the testing machine. A weight was placed on the brush, and the brush was slid back and forth over the cut sample 50 times.
Subsequently, the state of wear (chips of organic particles) on the surface of the cut sample was observed using SEM. Specifically, the surface was observed using a SEM (KEYENCE VHX-D510) set at an inclination angle of 60 degrees, and the durability of the surface layer was evaluated using the following evaluation criteria. The results are shown in Table 2.
(Evaluation criteria)
〇: No chipping was observed in the majority of the organic particles ×: Chips were observed in the majority of the organic particles

(7) Evaluation of antiviral properties The antiviral properties of Sample 1 of Example and Sample of Comparative Example 1 were evaluated according to JIS R1756 (2020) in the dark. Specifically, an antiviral test was conducted using bacteriophage Qβ, and the antiviral activity value (V) in the dark was calculated using the following formula.
Antiviral activity value: V=Log ₁₀ (UV/TV)
TV: Bacteriophage infectivity titer (pfu) 24 hours after dropping bacteriophage liquid
UV: bacteriophage infectivity value (pfu) immediately after dropping bacteriophage liquid
When the antiviral activity value was V≧2, the sample was judged to exhibit good antiviral properties. The results are listed in Table 2.

(8) Evaluation of anti-slip property <Surface roughness measurement>
For each sample, the arithmetic mean roughness (Ra) value of the surface layer was measured using a stylus surface roughness measuring device (SURFCOM 15OODX, manufactured by Tokyo Seimitsu Co., Ltd.). The measurement was performed three times for each sample, and the average value was taken as the surface roughness of the surface layer. The measurement conditions were as follows. The results are listed in Table 2.
(Measurement condition)
Measurement type: Roughness measurement Measurement length: 10mm
Cutoff wavelength: 0.25mm
Measurement range: ±128.0μm
Speed: 0.3mm/s
Cutoff type: Gaussian

<Evaluation of anti-slip property when wet>
Using a dropper, 2 mL of ion-exchanged water was dropped onto the surface of each sample, and the palm of the hand was pressed against the surface to evaluate the anti-slip properties when wet. The slip properties of the sample of Comparative Example 4 and the other samples were compared, and the anti-slip properties of the samples of Examples 1 to 4 and Comparative Examples 1 to 3 were evaluated based on the following criteria. The results are listed in Table 2.
(Evaluation criteria)
〇: Significantly less slippery than the sample of Comparative Example 4 △: Slightly less slippery than the sample of Comparative Example 4 ×: Anti-slip property equal to or lower than that of the sample of Comparative Example 4

(9) Evaluation of design <Measurement of gloss>
The glossiness of each sample at 60° was measured using a glossmeter (Nippon Denshoku Industries Co., Ltd. VG7000). The results are listed in Table 2.

<Visual appearance evaluation>
The appearance of each sample was visually evaluated according to the following criteria. The results are listed in Table 2.
(Evaluation criteria)
〇: Excellent matting properties △: Matting properties ×: Poor matting properties, causing shine

1: Water-related components 2: Base material 3: Surface layer 4: (meth)acrylic resin 5: Particles 6: Inorganic antiviral agent 7: Top surface of surface layer

Claims (13)

A plumbing member comprising a base material and a surface layer provided on the base material,
The surface layer includes a (meth)acrylic resin, particles, and an inorganic antiviral agent,
The particles are particles made of (meth)acrylic resin,
The inorganic antiviral agent includes an inorganic carrier and an inorganic active ingredient supported on the inorganic carrier,
A region between the outermost surface of the surface layer and a position 2 μm deep from the outermost surface perpendicularly to the substrate direction (hereinafter referred to as “2 μm region”), and within the 2 μm region, A water area in which the ratio of the volume of the inorganic antiviral agent contained in the target area to the volume of the area above the particles (hereinafter referred to as "target area") in which at least a portion of the particles are contained is 20% or more. Element. 1 . The total volume of the inorganic antiviral agent contained in the upper half region of the surface layer is 70% or more of the total volume of the inorganic antiviral agent contained in the entire region of the surface layer. Plumbing components described in . The plumbing member according to claim 1, wherein the volume average particle diameter of the inorganic carrier contained in the inorganic antiviral agent is smaller than the volume average particle diameter of the particles. The plumbing member according to claim 1, wherein the surface layer has a pencil hardness of 1H or more. The plumbing member according to claim 1, wherein the volume average particle diameter of the particles is larger than the thickness of the surface layer. The plumbing member according to claim 1, wherein the surface layer has a surface roughness Ra of 0.1 or more. The plumbing member according to claim 1, wherein the surface layer has a thickness of 5 μm or more and 20 μm or less. The plumbing member according to claim 1, wherein the particles are embedded in the surface layer. The plumbing member according to claim 1, wherein the amount of the particles contained in the surface layer is 10% by weight or more and 20% by weight or less. The inorganic carriers include zeolite, apatite, zirconia, zirconium phosphate, calcium phosphate, calcium zinc phosphate, silica gel, calcium silicate, magnesium aluminate silicate, titanium oxide, potassium titanate, silica, alumina, and soluble glass. The plumbing member according to claim 1, which is one or more members selected from the group consisting of , thiosulfite. The plumbing member according to claim 1, wherein the active ingredient is one or more selected from the group consisting of silver ions, copper ions, and zinc ions. The plumbing member according to claim 1, wherein the volume average particle diameter of the inorganic carrier contained in the inorganic antiviral agent is half or less of the average volume particle diameter of the particles. The plumbing member according to claim 1, wherein the amount of the inorganic antiviral agent contained in the surface layer is 0.3% by weight or more and 4% by weight or less.

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