JP7456240B2 - Water equipment - Google Patents

Description

TECHNICAL FIELD The present invention relates to a water-related device having a water-repellent layer on its surface, and more particularly to a water-related device used in an environment where water may be splashed.

Domestic water, including tap water, contains silicon and calcium, and these substances cause limescale. Plumbing equipment that comes into contact with domestic water is required to suppress the adhesion of limescale or to easily remove attached limescale. BACKGROUND ART In order to prevent stains such as limescale from adhering to the surfaces of plumbing equipment or to improve the removability of stains, techniques are known in which the surfaces of components are modified by coating them with a protective layer.

However, it was observed that by providing a protective layer, discoloration was observed, and the appearance of the member was impaired due to damage or peeling of the protective layer. On the other hand, since it is difficult to prevent dirt from adhering to the surface of plumbing members, dirt is removed by cleaning. When cleaning hard-to-remove stains such as limescale, methods such as polishing using special detergents are used, which is a burdensome task to perform on a daily basis. Therefore, there is a need to be able to remove dirt by simple cleaning.

Antifouling technology using a monomolecular film that is chemically bonded directly to a base material as a protective layer is known. For example, JP-A No. 2004-217950 (Patent Document 1) describes that easy removal of limescale can be obtained by coating the surface of a faucet fitting with fluoroalkylphosphonic acid. Further, by forming a monomolecular film, most of the hydroxyl groups on the surface of the base material are shielded, thereby preventing dirt from adhering to the surface of the base material, and making it possible to easily remove the dirt. For example, Japanese Unexamined Patent Publication No. 2000-265526 (Patent Document 2) describes that fixing of silicic acid scale stains is suppressed by providing an antifouling layer that shields hydroxyl groups on the surface of pottery. This antifouling layer is obtained by coating and drying a mixture of hydroxyl groups on the surface of the pottery, an organosilicon compound containing a fluorinated alkyl group, a methylpolysiloxane compound containing a hydrolyzable group, and an organopolysiloxane compound. ing.

Japanese Patent Application Publication No. 2004-217950 JP 2000-265526 A

Dirt such as water scale accumulates as a result of repeated adhesion and drying of the product during daily product use, which poses a problem in that the wiping force required to remove the stain becomes stronger and the number of times of wiping increases. Furthermore, even if a surface layer (for example, a monomolecular layer) is formed in areas that are frequently touched by users and cleaners, there is a problem that durability is poor because they are exposed to daily sliding movements.

The present inventors have discovered that by providing a dense and thin water-repellent surface layer on the surface of a plumbing device, sufficient durability for practical use can be obtained without impairing the texture of the plumbing device. The present invention is based on such knowledge.

The water-related equipment according to the present invention is
A substrate and a surface layer on the substrate,
the substrate is at least partially made of a metal, and has the surface layer on the metal portion;
The surface layer is water repellent, and is characterized in that the end point of the surface layer is a point at which, in a profile obtained by XPS depth direction analysis, the absolute value of the difference between the carbon atom concentration at a certain measurement point and the carbon atom concentration at the immediately preceding measurement point becomes 1.0 at % or less, and the sputtering time from the start of sputtering to the end point is within 5 minutes.

According to the present invention, a plumbing device with excellent durability is provided without impairing the quality of the plumbing device.

1 is a schematic diagram showing a basic configuration of a plumbing device according to the present invention; BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of a water faucet, which is an example of a plumbing device according to the present invention, showing the parts (lower surface and back surface) of the faucet to which the surface of the member according to the present invention is preferably applied.

The plumbing equipment 1 according to the present invention includes a base material 10 and a surface layer 30 on the base material 10, as shown in FIG. The member 1 may further include an intermediate layer 20 between the base material 10 and the surface layer 30.

Surface Layer The surface layer 30 in the present invention is a water-repellent layer containing organic molecules, and is transparent and thin enough not to impair the color of the substrate below the surface layer 30. By having a water-repellent surface layer, adhesion of water stains is suppressed in plumbing equipment that comes into contact with tap water containing silicon and calcium (substances that cause water stains), and any water stains that do adhere can be easily removed.

Material of Surface Layer In the present invention, the surface layer 30 may be a polymer layer, a low molecular layer, or a monomolecular layer.

Monomolecular layer In the present invention, the surface layer 30 is a layer containing a hydrophobic group R and a functional group X having coordination properties with respect to a metal element, and the surface layer 30 is a monomolecular layer formed of a single layer. is preferable, and self-assembled monolayers (SAM) consisting of RX are more preferable. A self-assembled monolayer is a layer in which molecules are densely assembled, so it has excellent water repellency.
The thickness of the SAM is approximately the same as the length of one constituent molecule. Here, "thickness" refers to the length of the SAM along the Z direction. Here, in FIG. 1, the direction from the base material 10 toward the surface layer 30 is defined as the Z direction. The thickness of the SAM is 10 nm or less, preferably 5 nm or less, more preferably 3 nm or less. Further, the thickness of the SAM is 0.5 nm or more, preferably 1 nm or more. By using constituent molecules whose SAM thickness falls within this range, the base material can be efficiently coated, and water-related equipment with excellent ease of removal of pollutants such as limescale can be obtained. I can do it.

In a preferred embodiment of the present invention, SAM is a molecular assembly formed on a solid surface during the process of adsorption of organic molecules to the solid surface, and the molecules constituting the assembly are densely assembled due to interactions between molecules. do. SAM contains hydrocarbon groups. As a result, hydrophobic interactions occur between the molecules and the molecules can be densely aggregated, making it possible to obtain plumbing equipment with excellent dirt removal properties.

In the present invention, the non-polymer organic ligand RX includes a hydrophobic group R and a functional group X having coordinating properties with respect to a metal element. The non-polymer organic ligand RX is bonded to the underlying surface via the functional group X. Here, "non-polymer" refers to Definition 1.1 (i.e., relative A molecule with a large molecular mass that has a structure composed of many repetitions of units that are obtained virtually or conceptually from molecules with a small relative molecular mass. http://main.spsj.or.jp/c19 /iupac/Recommendations/glossary36.html). SAM is a layer formed using such a non-polymer organic ligand RX.

Non-polymer organic ligand RX
In a preferred embodiment of the present invention, the surface layer 30 is a layer formed using a non-polymer organic ligand RX. The hydrophobic group R is preferably a hydrocarbon group consisting of C and H. Atoms other than carbon may be substituted at one or two positions within the skeleton of the hydrocarbon group R. Examples of substituted atoms include oxygen, nitrogen, and sulfur. Preferably, one end of R (the end that is not bonded to X) is a methyl group. This makes the surface of the plumbing equipment water repellent, making it easier to remove dirt.

Specific example of R (alkyl)
In the present invention, the hydrophobic group R is preferably a hydrocarbon group consisting of C and H. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further, it may be a chain hydrocarbon or may contain a cyclic hydrocarbon such as an aromatic ring. R is preferably a chain saturated hydrocarbon group, more preferably a straight chain saturated hydrocarbon group. Since the chain-type saturated hydrocarbon group is a flexible molecular chain, it can cover the intermediate layer without gaps, and can improve water resistance. When R is a chain hydrocarbon group, it is preferably an alkyl group having 6 or more and 25 or less carbon atoms. R is more preferably an alkyl group having 10 or more and 18 or less carbon atoms. When the number of carbon atoms is large, interaction between molecules is large, and the spacing between hydrophobic groups can be narrowed, and water resistance can be further improved.

In the present invention, the hydrophobic group R preferably does not contain a halogen atom, such as a fluorine atom. By forming the surface layer with a compound in which the hydrophobic group R does not contain a halogen atom, the sliding resistance can be improved.

Specific examples of X In the present invention, the functional group , a hydroxyl group, a hydroxyamide group, and an α- or β-hydroxycarboxylic acid group.

Carboxyl groups, β-diol groups, amino groups, hydroxyl groups, hydroxyamide groups, α- or β-hydroxycarboxylic acid groups coordinate (adsorb) with the metal elements contained in the intermediate layer without polymerizing with each other. , a dense surface layer is formed.

According to a preferred embodiment of the present invention, X is at least one type of functional group containing a phosphorus atom selected from a phosphonic acid group, a phosphoric acid group, and a phosphinic acid group, and more preferably a phosphonic acid group. Thereby, it is possible to efficiently obtain a member that has high water resistance and excellent ease of removing contaminants.

Specific examples of RX The organic phosphonic acid compound represented by the general formula RX is preferably octadecylphosphonic acid, hexadecylphosphonic acid, dodecylphosphonic acid, decylphosphonic acid, octylphosphonic acid, hexylphosphonic acid, More preferred are octadecylphosphonic acid, hexadecylphosphonic acid, dodecylphosphonic acid, and decylphosphonic acid. Even more preferred is octadecylphosphonic acid.

In R - Protocatechuic acid, gallic acid, dopa, catechol (orthohydroxyphenyl) group as a molecule with , amino acid as a molecule with an amino group, alcohol as a molecule with a hydroxyl group, hydroxamic acid as a molecule with a hydroxyamide group, α- or β-hydroxy Salicylic acid and quinic acid may be used as the molecule having a carboxylic acid group.

In the present invention, the surface layer 30 may be formed from two or more types of RX. The surface layer formed from two or more types of RX means a surface layer formed by mixing multiple types of the above-mentioned compounds. Furthermore, in the present invention, the surface layer 30 may contain a trace amount of organic molecules other than RX, as long as the easy removal of limescale is not impaired.

Intermediate layer According to a preferred embodiment of the present invention, the intermediate layer 20 may be provided below the surface layer 30. The intermediate layer 20 can obtain good adhesion to the surface layer 30 and the base material 10. A preferable example of the intermediate layer 20 is a layer containing metal atoms and oxygen atoms. In the intermediate layer 20, the metal atoms are bonded to oxygen atoms. That is, the intermediate layer 20 contains the metal element in an oxidized state. In the present invention, it is preferable that the material is at least one selected from the group consisting of Cr, Zr, and Si. Furthermore, the intermediate layer 20 preferably has a thickness that is approximately the same as or less than that of the surface layer 30 so as not to impair the color of the base layer.

Substrate In the present invention, the material of the substrate is not particularly limited, and for example, materials commonly used as substrates for plumbing equipment can be used.

Region 10a of base material 10
The base material 10 includes a support material 10a. The material of the support member 10a may be metal, resin, ceramic, earthenware, or glass.

Region 10b of base material 10
The base material 10 includes a region 10b when the material of the support material 10a is other than metal. Moreover, the base material 10 may be provided with the area|region 10b when the material of the support material 10a is metal. The region 10b is, for example, a layer containing metal or a layer made of an inorganic compound containing carbon, formed by metal plating or physical vapor deposition (PVD). The region 10b may be composed only of a metal element, or may be made of a metal nitride (for example, TiN, TiAlN, etc.), a metal carbide (for example, CrC, etc.), a metal carbonitride (for example, TiCN, CrCN, ZrCN, etc.). ZrGaCN, etc.). Region 10b may be formed directly on support material 10a, or may include different layers between region 10b and support material 10a. An example of the base material 10 on which the region 10b is provided is a metal-plated product in which the region 10b is provided on a support material 10a made of brass or resin by metal plating. On the other hand, examples of the base material 10 in which the region 10b is not provided include a metal molded product such as stainless steel (SUS). The surface texture of the base material 10 is not particularly limited, but preferably has a three-dimensional shape.

In the present invention, region 10b may have a multilayer structure. For example, the region 10b may include a colored layer on a layer made of a metal element such as plating. The colored layer is a layer exhibiting a color in which the absolute value of at least one of ΔL*, Δa*, and Δb* on the surface of the member having the colored layer exceeds 0, compared to the surface of the member having no colored layer. The colored layer is preferably a layer containing Zr or C. By configuring the region 10b in this manner, it is possible to express various metallic textures. In the present invention, it is more preferable that the colored layer is an inorganic layer containing Zr or C, since the member has excellent durability.

When the surface layer is made of an organic phosphonic acid compound, the region 10b preferably includes a layer containing oxygen atoms and one or more metal atoms selected from Ti, Zr, Cr, and Al.

Identification of Member Configuration To identify the member in the present invention, first, the elements constituting the surface layer 30 are identified by XPS measurement, and the presence of the hydrophobic group R and the functional group X is confirmed by mass spectrometry. Further, the thicknesses of the surface layer 30 and the intermediate layer 20 are confirmed by sputtering while measuring the abundance ratio of elements by XPS measurement. Next, to identify the colored layer 20 and the base material 10, their presence and boundaries are identified by observing the cross section with a SEM. Before the above measurements, pretreatment is performed to remove dirt adhering to the surface.

Pretreatment In the present invention, the surface of the plumbing equipment is cleaned before measurement to sufficiently remove dirt adhering to the surface. For example, after wiping cleaning with ethanol and sliding cleaning with a sponge using a neutral detergent, thorough rinsing is performed with ultrapure water. In addition, in the case of plumbing equipment with a large surface roughness, such as hairline processing or shot blasting, select a flat part with the highest possible smoothness for measurement. A highly smooth part refers to a point where L* is less than 5 according to the SCE method, which does not include a specular reflection component when color difference is measured because it diffuses light more than a rough part.

Identification of surface layer (1) Certification of R and X of surface layer

In the present invention, the surface layer is confirmed in detail by the following procedure. First, surface elemental analysis is performed using XPS analysis to confirm the elements contained in the surface layer. Next, the molecular structure is identified by mass spectrometry based on the mass-to-charge ratio (m/z) derived from the molecules of the components present on the surface. For mass spectrometry, time-of-flight secondary ion mass spectrometry (TOF-SIMS) or high-resolution mass spectrometry (HR-MS) can be used. Here, high-resolution mass spectrometry refers to a method that can measure with a mass resolution of 0.0001 u (unified atomic mass units) or less than 0.0001 Da, and can estimate elemental composition from accurate mass. HR-MS includes double convergence mass spectrometry, time-of-flight tandem mass spectrometry (Q-TOF-MS), Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), and orbitrap mass spectrometry. In the present invention, time-of-flight tandem mass spectrometry (Q-TOF-MS) is used. For mass spectrometry, HR-MS is preferably used if sufficient amounts of R and X can be recovered from the member. On the other hand, if a sufficient amount of R and X cannot be recovered from a member due to the small size of the member, it is desirable to use TOF-SIMS. When using mass spectrometry, the presence of R and X can be confirmed by detecting the ion intensity of m/z corresponding to ionized R and X. Here, the ion intensity is detected by having a signal that is more than three times the average value of 50 Da around the m/z that has the lowest value in the range in which the ion intensity is calculated in the measurement range. I reckon.

(2) TOF-SIMS measurement conditions for surface layer R and The measurement conditions were: primary ions to be irradiated: 209Bi3++, primary ion acceleration voltage 25 kV, pulse width 10.5 or 7.8 ns, bunching, no charge neutralization, post-acceleration 9.5 kV, measurement range (area): approximately 500× 500 μm2, secondary ions to be detected: Positive, Negative, Cycle Time: 110 μs, number of scans is 16. As a measurement result, a secondary ion mass spectrum (m/z) derived from R and X is obtained. The secondary ion mass spectrum is expressed as the mass-to-charge ratio (m/z) on the horizontal axis and the intensity (count) of detected ions on the vertical axis.

(3) HR/MS measurement conditions for surface layer R and . For the measurement, for example, the cut out base material is immersed in ethanol, the components (R and Then measure. The measurement conditions are, for example, ion source: ESI/Duo Spray Ion Source, ion mode (Positive/Negative), IS voltage (-4500V), source temperature (600°C), DP (100V), MS at CE (40V). /Perform MS measurement. An MS/MS spectrum is obtained as a measurement result. The MS/MS spectrum is expressed as the mass-to-charge ratio (m/z) on the horizontal axis and the intensity (count) of detected ions on the vertical axis.

(4) Measurement of each atomic concentration The composition of the surface layer of each sample is determined by X-ray photoelectron spectroscopy (XPS). Before measurement, the sponge was rubbed with a neutral detergent and then thoroughly rinsed with ultrapure water. It is preferable to use PHI Qantera II (manufactured by ULVAC-PHI) as the XPS device. A spectrum is obtained by measuring each element under the following "Conditions for measuring element fraction by XPS" and "Conditions 1 for XPS sputter analysis".
The concentration of the detected atoms is calculated from the obtained spectrum using data analysis software PHI MultiPuk (manufactured by ULVAC-PHI). The obtained spectrum is calculated by calculating the peak area intensity after removing the background using the Shirely method for the peak based on the electron orbit of each measured atom, and using the device-specific sensitivity coefficient preset in the data analysis software. Correction processing is performed by dividing by . The ratio of the corrected peak area of a certain element to the sum of the corrected peak area intensities of all the measured element types is defined as the target atomic concentration, and at. Calculate in %.

Measurement conditions of element fraction by XPS X-ray conditions: Monochromatic AlKα ray, 25W, 15kV
Analysis area: 100μmφ
Neutralization gun conditions: 1.0V, 10μA
Photoelectron extraction angle: 45°
Time Per Step: 50ms
Sweep: 5 times Pass energy: 112eV
Analysis elements (energy range): Zr3d (177-187eV), C1s (281-296eV), N1s (394-406eV), O1s (524-540eV), Cr2p3 (572-582eV), Ti2p (452-463eV), Si2p (98-108eV)

Condition 1 for XPS sputter analysis (hereinafter referred to as "sputter condition 1")
Inert gas type: Ar
Sputter voltage: 500V
Sputtering range: 2mm x 2mm
Sputtering interval: 10 seconds Note that the sputtering voltage refers to the voltage applied to the Ar ion gun, and the sputtering range refers to the range of the surface to be scraped by sputtering. Moreover, the sputtering cycle refers to the time during which Ar gas is continuously irradiated for each measurement in the depth direction, and the sum of the sputtering cycles is the sputtering time.

(5) Identification of the thickness of the surface layer In the XPS measurement of the surface layer under sputtering condition 1, the absolute value of the difference between the carbon atom concentration at a certain measurement point and the carbon atom concentration at the previous measurement point is determined. The point at which the concentration is 1.0 at % or less is defined as the end point of the surface layer, and the sputtering time from the start of sputtering to the end point is within 5 minutes, preferably within 3 minutes. This time becomes an indicator of the thickness of the surface layer.

Preferable carbon atom concentration of surface layer 30 In the present invention, the carbon atom concentration of surface layer 30 is preferably 35 at% or more, more preferably 40 at% or more, still more preferably 43 at% or more, and most preferably It is 45 at% or more. Further, the carbon atom concentration is preferably less than 70 at%, more preferably 65 at% or less, and still more preferably 60 at% or less. A suitable range for the carbon atom concentration can be determined by appropriately combining these upper and lower limits. By setting the carbon atom concentration within such a range, easy removal of scale can be improved.

Preferred phosphorus atom concentration in surface layer 30 In the present invention, the phosphorus atom concentration in surface layer 30 is preferably 1.0 at% or more and less than 10 at%. Setting the phosphorus atom concentration within this range indicates that the surface layer 30 is dense. This makes it possible to obtain plumbing equipment that has sufficient water resistance and is easily removable. More preferably, the phosphorus atom concentration is 1.5 at% or more and less than 10 at%. This can further improve water resistance and ease of removing limescale.

Water repellency The water-related equipment of the present invention has a water droplet contact angle on its surface, preferably 90° or more, more preferably 100° or more. The water drop contact angle means a static contact angle, and is determined by dropping a 2 μl water drop onto a substrate and photographing the water drop from the side of the substrate 1 second later. As the measuring device, for example, a contact angle meter (model number: SDMs-401, manufactured by Kyowa Interface Science Co., Ltd.) can be used.

Identification of Intermediate Layer In the present invention, the existence of an intermediate layer can be identified by XPS depth direction analysis. First, perform XPS measurement for 10 minutes under sputtering condition 1, and at the point where the difference in detection of carbon atoms from the previous measurement point is 1.0 at% or less, check for metal elements detected at 10 at% or more. . If the concentration of the element becomes 3.0 at % or less after 10 minutes of sputtering, the range in which the element exists can be recognized as an intermediate layer. If the concentration of the element does not decrease to 3.0 at % or less after 5 minutes of sputtering, it is determined that the member is not provided with an intermediate layer.

Qualification of colored layer and base material The base material that may include the colored layer is cut in the cross-sectional direction, and the cross-section is milled using an ion milling device to obtain a smooth cross-section. By observing this cross section using a scanning electron microscope/energy dispersive X-ray spectroscopy (SEM/EDX), the colored layer and the base material can be identified. A SEM image is acquired in the observation area so that the colored layer and the base material are included. By performing a mapping analysis using EDX on the SEM image, the element distribution of the colored layer and the base material can be visually confirmed. This boundary surface with different element distribution is identified as the boundary surface between the colored layer and the base material.

Applications of Members In the present invention, plumbing equipment refers to equipment used in water supply and drainage equipment for buildings, preferably indoor equipment. Preferably, the surface layer of the present invention is used in an environment where water (for example, domestic water or industrial water) can come into contact with the surface layer and where the water can dry.

In the present invention, environments that can be exposed to water include places where water is used, such as residences, public facilities such as parks, commercial facilities, and offices, and such places are preferably bathrooms and toilet spaces. , restrooms, washrooms, kitchens, etc.

In the present invention, indoor equipment is equipment that is used in public facilities such as residences and commercial facilities and that is touched by people, preferably in bathrooms, toilet spaces, restrooms, washrooms, or kitchens. This is the equipment used. Examples of the indoor equipment of the present invention include products that are plated or coated with PVD. Specifically, faucets, drain fittings, water stop fittings, basins, doors, shower heads, shower bars, shower hooks, shower hoses, handrails, towel hangers, kitchen counters, kitchen sinks, drain baskets, kitchen hoods, and ventilation fans. Examples include drains, toilet bowls, urinals, warm water flush toilet seats, warm water flush toilet seats, toilet lids, warm water flush toilet seat nozzles, operation panels, operation switches, operation levers, handles, doorknobs, etc. The plumbing equipment of the present invention includes faucets, faucet fittings, drain fittings, water stop fittings, basins, shower heads, shower bars, shower hooks, shower hoses, handrails, towel hangers, kitchen counters, kitchen sinks, and drainage baskets. It is preferable that In particular, the plumbing equipment of the present invention can be suitably used as a member used in a bathroom or toilet space. Since these products are used in applications where domestic water comes into contact with the surface of the components, water scales are likely to form on the surfaces, and by using the components of the present invention as these products, the effects of the present invention can be particularly utilized. , dirt such as accumulated limescale can be removed with less force or fewer times of wiping.

Moreover, the surface of the plumbing equipment of the present invention is applied as the upper surface or side surface of a member constituting a toilet or a member constituting a bathroom. The surfaces or side surfaces of these members are the parts where the texture is most important and are the parts that are frequently cleaned. Furthermore, since it is a part of a water faucet that includes an operating part such as a handle, it is also the part that the user touches most. Therefore, the effects of the present invention can be maximized by applying the surface layer of the present invention to the relevant region.

The areas where the present invention is most effective include, for example, the top and front portions of a wall-mounted single-lever faucet as shown by the arrow in FIG. 2. Specifically, the top surface of the spout, the side surface of the main body, the top surface of the lever handle, etc. are included. Since these areas are areas where the texture and cleanliness of the faucet's surface are important, the sliding load during cleaning is high. By providing the surface layer shown in the present invention in such areas, excellent cleanability can be maintained for a long period of time, and the initial appearance of the member can be maintained.

The invention will be explained in further detail by the following examples. Note that the present invention is not limited to these examples.

Example 1
A brass plate was nickel-plated and then chromium-plated to prepare a substrate.
Next, a surface layer having a hydrocarbon group was formed by the following procedure.
First, in order to remove dirt present on the surface of the substrate, the substrate was ultrasonically cleaned with an aqueous solution containing an alkaline detergent, and then the substrate surface was exposed to running water to remove the detergent.Furthermore, the substrate was immersed in ion-exchanged water, and rinsed by ultrasonic cleaning, and then the moisture was removed with an air duster.
Next, the substrate was immersed in a 2.5 M aqueous sodium hydroxide solution at 50° C. for 5 minutes, and then thoroughly rinsed with ion-exchanged water.
A solution of octadecylphosphonic acid (ODPA) (product code: O0371, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Wako First Grade) was used as the treatment agent for forming the surface layer. The substrate was immersed in the treatment agent for at least one minute, and then washed with ethanol. It was then dried in a dryer at 120°C for 10 minutes to form an organic layer on the substrate surface. In this way, the member of Example 1 was produced.

( Comparative example 2)
A base material was prepared by nickel plating a brass plate and then chromium plating.
Next, a surface layer comprising fluorocarbon groups was formed by the following procedure.
First, in order to remove dirt present on the surface of the base material, ultrasonic cleaning was performed using an aqueous solution containing an alkaline detergent, and then the detergent was removed by exposing the surface of the base material to running water. Furthermore, after immersing in ion-exchanged water and rinsing with ultrasonic cleaning, moisture was removed with an air duster.
Next, the substrate was irradiated with ultraviolet light (wavelength: 254 nm, irradiation intensity: about 15 mW/cm ² ) for 10 minutes.
Then, a solution of a silicone primer (product name: KBM403, manufactured by Shin-Etsu Chemical) dissolved in isopropyl alcohol (manufactured by Fujifilm Wako Pure Chemical Industries) was soaked into the nonwoven fabric (product name: Bencot M3-II, manufactured by Asahi Kasei). After spreading it over the entire base material, it was air-dried for 10 minutes to form an intermediate layer.
As a treatment agent for forming the surface layer, a coating agent containing a fluorinated alkyl group (product name: SURECO2101S, manufactured by AGC) was used. This treatment agent was impregnated into a nonwoven fabric (product name: Bemcot M3-II, manufactured by Asahi Kasei), spread over the entire substrate, and then dried in a dryer at 120° C. for 30 minutes.
In this way, a member of Comparative Example 2 was produced.

(Example 3)
A surface layer was formed on the top surface of the wall-mounted single-lever faucet (product number: TKS05315J, manufactured by TOTO) in FIG. 2 in the same manner as in Example 1 to produce the member of Example 3.

(Comparative example 1)
A base material was prepared by nickel plating a brass plate and then chromium plating.
Next, a surface layer comprising fluorocarbon groups was formed by the following procedure.
First, in order to remove dirt present on the surface of the base material, ultrasonic cleaning was performed using an aqueous solution containing an alkaline detergent, and then the detergent was removed by exposing the surface of the base material to running water. Furthermore, after immersing in ion-exchanged water and rinsing with ultrasonic cleaning, moisture was removed with an air duster.
Next, the substrate was irradiated with ultraviolet light (wavelength: 254 nm, irradiation intensity: about 15 mW/cm2) for 10 minutes.
Then, a solution of a silicone primer (product name: KBM403, manufactured by Shin-Etsu Chemical) dissolved in isopropyl alcohol (manufactured by Fujifilm Wako Pure Chemical Industries) was soaked into the nonwoven fabric (product name: Bencot M3-II, manufactured by Asahi Kasei). After applying and spreading it over the entire substrate, it was heated and dried at 120° C. for 5 minutes. Further, the application and drying of the primer solution was repeated twice to form an intermediate layer.
As a treatment agent for forming the surface layer, a coating agent containing a fluorinated alkyl group (product name: SURECO2101S, manufactured by AGC) was used. This treatment agent was impregnated into a nonwoven fabric (product name: Bemcot M3-II, manufactured by Asahi Kasei), spread over the entire substrate, and then dried in a dryer at 120° C. for 30 minutes.
In this way, the member of Comparative Example 1 was produced.

Each member produced as described above was used as a sample, and the following tests were conducted.

Measurement of each atomic concentration In the XPS measurement under the above "sputtering condition 1", the point where the difference in the detection of carbon atoms from the previous measurement point became 1.0 at % or less was determined as the end point of the surface layer, and the sputtering time up to that point is shown in Table 1.

Limescale removability test 200 μl of tap water was dropped onto the surface of each sample heated to 50° C. in a drying oven and left until the liquid was dry. This operation was defined as one cycle. The same operation was repeated, that is, more tap water was dropped onto the limescale formed after one cycle, and it was dried to form limescale for two cycles. Furthermore, the same operation was repeated to produce water scales for 3 and 5 cycles. The samples on which water scale was formed were evaluated according to the following procedure.

(i) Using a dry cloth, the surface of the sample was slid back and forth 5 times while applying a light load (80 gf/cm2).
(ii) If removal of limescale can be confirmed, the test is terminated. If limescale residue was present, repeat (i).
The ability to remove limescale was determined by rinsing the surface of the sample with running water, removing water with an air duster, and visually determining whether limescale remained on the surface of the sample.

The scale removal performance was evaluated as follows based on the number of sliding movements required to remove scale by the steps (i) and (ii).
3 points if removed in 5 times 2 points if removed in 10 times 1 point if removed in 15 times 0 point if not removed in 15 times The evaluation results are listed in Table 1.

Removal of sebum stains The sebum stain solutions listed in Table 2 were applied thinly to the glass surface using a rag. The sebum stain solution on the glass was transferred onto a urethane sponge (manufactured by 3M) cut into 1 cm ³ pieces and stamped on the surface of the sample to attach the sebum stain.
(i) Using a damp cloth, the surface of the sample was slid back and forth 5 times while applying a light load (50 gf/cm ² ).
Items that could be removed in step (i) were marked as "○", and items that could not be removed in step (i) were marked as "x". Note that whether or not sebum stains could be removed was determined visually. The evaluation results are shown in Table 1 as sebum stain removability/initial stage.

Water Contact Angle Measurement Before measurement, each sample was scrubbed with a urethane sponge using a neutral detergent and thoroughly rinsed with ultrapure water. A contact angle meter (model number: SDMs-401, manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the water droplet contact angle of each sample. Ultrapure water was used for measurement, and the size of the dropped water droplet was 2 μl. The contact angle is a so-called static contact angle, and the value was taken 1 second after dropping water, and the average value of measurements taken at five different locations was calculated. However, if an abnormal value appeared among the five locations, the average value was calculated by excluding the abnormal value. The measurement results are shown in Table 1 as water contact angle/initial.

Water Resistance Test After each sample was immersed in 70°C hot water for 120 hours, the surface of the sample was rinsed with running water, and moisture was removed using an air duster. For each sample after the water resistance test, the removability of limescale stains after one cycle of limescale was formed was evaluated. The evaluation results are shown in Table 1 as after the scale removability/water resistance test. In addition, the surface of the sample after the water resistance test was visually observed. Items in which abnormalities were observed after being immersed in hot water were rated "×". Moreover, those in which no abnormality was observed after being immersed in warm water were rated "○". The results are shown in Table 1.

Sliding Resistance Test The surface of each sample was slid 3000 times using a melamine sponge, with the melamine sponge soaked in water, while applying a load (200 gf/cm ² ) to the sample surface. After sliding, the sample surface was rinsed with running water and moisture was removed with an air duster. After sliding, each sample was evaluated for water contact angle measurement and sebum stain removability. The evaluation results are shown in Table 1 after the water contact angle/sliding resistance test and after the sebum stain removability/sliding resistance test.

Water Resistance Test 2_Evaluation of Appearance After each sample 1 to 22 was immersed in warm water at 90° C. for 1 hour, the sample was taken out and the hot water adhering to the sample was immediately removed with an air duster. After removing the hot water, the sample was left indoors and cooled to room temperature, and then the surface of the sample was visually observed. Items in which abnormalities were observed after being immersed in warm water were rated "×". Moreover, those in which no abnormality was observed after being immersed in warm water were rated "○". The results are shown in Table 1.

Reference Signs List 10 base material, 10a one region of base material 10, 10b another region of base material 10, 20 intermediate layer 30 surface layer

Claims (3)

comprising a substrate and a surface layer on the substrate,
The base material has at least a part made of metal, and the surface layer is provided on the part made of the metal,
The surface layer includes a hydrophobic group R that does not contain a halogen atom, and a functional group X that has coordinating properties with respect to a metal atom,
The surface layer is water repellent and has a certain measurement point in the profile obtained by XPS depth direction analysis measured under the following conditions of "Measurement conditions of element fraction by XPS" and "Sputtering conditions 1". The point where the absolute value of the difference between the carbon atom concentration at and the carbon atom concentration at the previous measurement point is 1.0 at% or less is the end point of the surface layer, and the sputtering time from the start of sputtering to the end point is within 5 minutes,
Plumbing equipment used as faucets, components of toilets, or components of bathrooms,
Plumbing equipment, the surface of which is applied as the top or front surface of the faucet, a member constituting a toilet, or a member constituting a bathroom .

Conditions for measuring elemental fractions by XPS
X-ray conditions: monochromatic AlKα ray, 25W, 15kV
Analysis area: 100μmφ
Neutralization gun conditions: 1.0V, 10μA
Photoelectron extraction angle: 45°
Time Per Step: 50ms
Sweep: 5 times
Pass energy: 112eV
Analysis elements (energy range): Zr3d (177-187eV), C1s (281-296eV), N1s (394-406eV), O1s (524-540eV), Cr2p3 (572-582eV), Ti2p (452-463eV), Si2p (98-108eV)

Sputtering conditions 1
Inert gas type: Ar
Sputter voltage: 500V
Sputtering range: 2mm x 2mm
Sputter interval: 10 seconds 2. The plumbing equipment according to claim 1, wherein the surface layer has a non-polymer organic ligand RX bonded to the underlying surface via a functional group X. The plumbing equipment according to claim 2, wherein the functional group X is at least one selected from a phosphonic acid group, a phosphoric acid group, and a phosphinic acid group.