JP7358886B2 - sanitary equipment parts - Google Patents

Description

The present invention relates to a sanitary equipment member comprising a base material containing a metal element on at least the surface thereof, and preferably relates to a sanitary equipment member used indoors or in an environment where it may be splashed with water.

Indoors, metal members are used for parts that are frequently touched by hands, such as handles and levers. As a result, fingerprints and other sebum stains adhere to the surface, impairing its appearance. These stains can be cleaned by wiping, but they are highly viscous and are stretched by wiping, requiring repeated scrubbing to remove them, making cleaning a major burden. Therefore, there is a need to be able to remove sebum stains with simple cleaning.

Furthermore, members used around water (also referred to as water-related members) are used in an environment where water is present. Therefore, water tends to adhere to the surface of the water-related member. It is a known problem that when the water adhering to the surface dries, limescale containing silica and calcium, which are components contained in tap water, is formed on the surface of the plumbing member. It is also known that stains such as proteins, sebum, mold, microorganisms, soap, etc. adhere to the surfaces of plumbing components.

Since it is difficult to prevent these stains from adhering to the surfaces of plumbing components, it is customary to remove the stains from the surfaces by cleaning to restore the original condition. Specifically, these stains are removed by using detergent and tap water and rubbing the surface of the plumbing parts with a cloth or sponge. Therefore, plumbing parts are required to be easy to remove dirt, that is, easy to remove.

Plumbing components are also required to have a high level of design. In particular, a metal member containing a metal element on its surface is preferably used for the surface of a plumbing member due to its beautiful appearance. Therefore, it is required to provide metal members with easy removability without impairing their design.

In this regard, a limescale removal technique using a water-repellent antifouling layer is known. JP-A No. 2000-265526 describes that the fixation of silicic acid scale stains can be 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.

Furthermore, JP-A No. 2004-217950 discloses a surface treatment agent for plating film containing a fluorine-containing compound containing a fluorine-containing group and a group having complex-forming ability for a plated surface such as a water faucet. It is stated that easy removal of limescale can be obtained by treating with .

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

Neither the antifouling layer described in JP-A No. 2000-265526 nor the surface treatment described in JP-A No. 2004-217950 had sufficient performance in terms of easy removal of dirt and its sustainability. SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a sanitary equipment member that is easy to remove dirt and has excellent durability.

The present inventors proposed an organic layer provided on a base material at least whose surface contains a metal element by the general formula R-X (R is a hydrocarbon group or an atom other than carbon at one or two positions within the hydrocarbon group). and X is at least one selected from a phosphonic acid group, a phosphoric acid group, and a phosphinic acid group. It has been found that by forming an organic layer through a metal oxide layer formed in the above method, it is possible to easily remove stains and to make the stains last longer. The present inventors completed the present invention based on this knowledge. That is, the present invention
a base material whose surface contains a metal element;
a metal oxide layer formed on the base material;
A sanitary equipment member comprising an organic layer provided on the metal oxide layer,
The metal element is at least one selected from the group consisting of Cr, Zr, and Ti,
The organic layer is present on the surface of the sanitary equipment member,
The sanitary equipment member has a surface that is
When measured by X-ray photoelectric spectroscopy (XPS) using wide scan analysis according to condition 1, the metal element (M), phosphorus atom (P), oxygen atom (O), and carbon atom (C ) is detected, and
When measured according to condition A by time-of-flight secondary ion mass spectrometry (TOF-SIMS), the general formula RX (R is a hydrocarbon group or an atom other than carbon at one or two positions in the hydrocarbon group) and X is at least one selected from phosphonic acid group, phosphoric acid group, and phosphinic acid group) is detected,
The sanitary equipment member is characterized in that limescale is removed in a test conducted using the following test method.
(Condition 1)
X-ray conditions: Monochromatic AlKα rays (output 25W)
Photoelectron extraction angle: 45°
Analysis area: 100μmφ
Operation range: 15.5-1100eV
(Condition A)
Primary ions to be irradiated: ²⁰⁹ Bi ₃ ⁺⁺
Primary ion acceleration voltage: 25kV
Pulse width: 10.5or7.8ns
Bunching: Yes Charge neutralization: None Post-stage acceleration: 9.5kV
Measurement range (area): Approximately 500 x 500 μm ²
Secondary ions to detect: Positive and Negative
Cycle time: 110μs
Number of scans: 16
(Test method)
Perform the following steps 1) to 4) in that order.
1) After immersing the sanitary equipment member in hot water at 70°C for 2 hours, the surface is rinsed with running water, and then the water on the surface is removed.
2) Drop 20 μl of tap water onto the surface of the sanitary equipment member and leave it indoors for 24 hours to form limescale on the surface of the sanitary equipment member.
3) Slide a dry cloth back and forth 10 times on the surface where limescale has been formed while applying a load of 100 gf/cm ² .
4) Visually judge whether water scale has been removed from the surface after sliding.

According to the present invention, it is possible to provide a sanitary equipment member that is easy to remove dirt and has excellent durability.

1 is a schematic diagram showing the structure of a sanitary equipment member of the present invention in which an organic layer is formed on a base material. FIG. 2 is a schematic diagram showing, at a molecular level, an organic layer formed on a base material in the sanitary equipment member of the present invention. FIG. 2 is a schematic diagram showing, at a molecular level, an organic layer formed on a base material in a conventional metal member. The C1s spectrum obtained by XPS analysis of sample 3 is shown. The P2p spectrum obtained by XPS analysis of sample 3 is shown. The depth profile of carbon atom concentration obtained by XPS analysis using argon ion sputtering of sample 3 is shown. The depth profile of carbon atom concentration obtained by XPS analysis using an argon gas cluster ion beam (Ar-GCIB) of Sample 3 is shown. The mass spectra ((a) positive, (b) negative) obtained by Q-TOF-MS/MS analysis of sample 3 are shown. A secondary ion mass spectrum (negative) obtained by TOF-SIMS analysis of sample 3 is shown. The Raman spectra ((a) 180-4000 cm ⁻¹ , (b) 280-1190 cm ⁻¹ ) obtained by SERS Raman analysis of Sample 3 are shown.

The sanitary equipment member of the present invention comprises a base material at least whose surface contains a metal element, a metal oxide layer formed on the surface of the base material, and a sanitary equipment member provided on the metal oxide layer, and A sanitary equipment member comprising an organic layer provided on a surface of the equipment member, wherein the metal element is at least one selected from the group consisting of Cr, Zr, and Ti; When the surface was measured using wide scan analysis using X-ray photoelectric spectroscopy (XPS), it was found that the metal element (M), phosphorus atom (P), oxygen atom (O), and carbon atom (C) was detected and measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS). and X is at least one selected from a phosphonic acid group, a phosphoric acid group, and a phosphinic acid group. After being immersed in water for 2 hours, water scale was removed in a water scale stain removability test.

A metal oxide layer is required in order for the compound represented by RX to be bonded to the surface of the sanitary equipment member. The surface of the metal oxide layer is hydrophilic, but by forming an organic layer on the surface, it becomes water repellent and exhibits limescale adhesion prevention performance. Therefore, it was thought that it would be better to form the organic layer using a fluorine-containing compound as described in JP-A-2004-217950 because a highly water-repellent surface can be obtained. However, the inventors have found that the surface of an organic layer formed using a fluorine-containing compound has low limescale adhesion prevention performance. This is due to the combined effect of the extremely high water repellency of the fluoroalkyl group, which acts as a repulsive force against water, and the hydrophilic metal oxide layer, which acts as an attractive force towards water. It is presumed that this is because the water penetrates into the organic layer and promotes the bonding between inorganic components (silicates, etc.) dissolved in water and metal oxides, thereby promoting the adhesion of limescale.

On the other hand, when an organic layer is formed using a compound that does not contain fluorine, such as an alkylphosphonic acid with a straight-chain hydrocarbon group, the ability to prevent limescale adhesion is high and stains can be easily removed. The inventors have found that (first effect). This is because an organic layer formed using a compound that does not contain fluorine has lower water repellency than an organic layer formed using a fluorine-containing compound, so water tends to penetrate into the metal oxide layer side. It is assumed that this is because it is weak.

Furthermore, being able to prevent water from entering the organic layer is considered to be advantageous in increasing the durability of the organic layer. The bond between RX and the metal oxide can be hydrolyzed by the presence of water. Therefore, in the case of an organic layer formed using a fluorine-containing compound etc. that is easily penetrated by water, if used in an environment where water is present, R-X will desorb from the metal oxide, reducing the ease of stain removal. The inventors also found that it could not be sustained.

On the other hand, by using an alkylphosphonic acid or the like having a straight-chain hydrocarbon group that can prevent water from entering, the bond between R-X and the metal oxide is made less likely to be hydrolyzed. Easily removable stains can be maintained. Furthermore, since the metal oxide layer contains at least one metal element (M) selected from the group consisting of Cr, Zr, and Ti, a stable bond (M -OP bond) can be formed. Therefore, even if a small amount of water enters the organic layer, it is possible to suppress the detachment of RX due to hydrolysis of the bond between RX and the metal oxide. Such stable M--O--P bonds provide the organic layer with durability when used in an environment where water is present or when rubbed for cleaning (second effect).

From the above, the sanitary equipment member of the present invention has both easy removal of dirt (first effect) and durability of the organic layer (second effect), thereby ensuring sufficient sustainability. It is possible.

Detailed embodiments of the present invention will be described below.

As shown in FIG. 1, the sanitary equipment member of the present invention includes a base material 70 whose surface at least contains a metal element, a metal oxide layer 20 containing the metal element, and a metal oxide layer 20 provided on the metal oxide layer 20. A sanitary equipment member 100 including an organic layer 10. The direction from the base material 70 toward the organic layer 10 is defined as the Z direction. The base material 70, the metal oxide layer 20, and the organic layer 10 are arranged in this order in the Z direction.

In the present invention, the organic layer 10 is a layer formed using RX, which will be described later, and is preferably a monolayer, and preferably a self-assembled monolayer (SAM). More preferred. Since the self-assembled monolayer is a layer in which molecules are densely assembled, most of the hydroxyl groups present on the surface of the metal oxide layer can be shielded. Molecules capable of self-assembly have a surfactant structure, and have a functional group (head group) that has a high affinity with the metal oxide layer and a site that has a low affinity with the metal oxide layer. Surfactant molecules having a phosphonic acid group, a phosphoric acid group, or a phosphinic acid group as a head group have the ability to form a SAM on the surface of a metal oxide layer. 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 in the Z direction, and does not necessarily mean the length of RX itself. 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 that allow the SAM thickness to fall within this range, it is possible to efficiently coat the metal oxide layer and obtain sanitary equipment members with excellent contaminant removability. can.

In the present invention, SAM is an aggregate of molecules formed on the surface of a base material during the process of adsorption of organic molecules to a solid surface, and the molecules forming the aggregate are densely assembled due to interactions between molecules. obtain. In the present invention, SAM contains hydrocarbon groups. As a result, hydrophobic interaction occurs between the molecules and the molecules can be densely aggregated, so that it is possible to obtain a sanitary equipment member with excellent stain removability.

In the present invention, SAM has the general formula RX (R is a hydrocarbon group or a group having atoms other than carbon at 1 or 2 positions in the hydrocarbon group, and X is a phosphonic acid group, a phosphoric acid group, and This layer is formed using a compound represented by at least one type selected from phosphinic acid groups.

In the present invention, the organic layer 10 is a layer formed using RX. R is a hydrocarbon group consisting of C and H. Further, R may have atoms other than carbon at one or two positions within the hydrocarbon group. The carbon number of R is preferably 6 or more and 25 or less, more preferably 10 or more and 18 or less. Examples of substituted atoms include oxygen, nitrogen, and sulfur. Preferably, one end of R (the end that is not bonded to X) consists of C and H, and is, for example, a methyl group. This makes the surface of the sanitary equipment member water-repellent, making it easier to remove dirt.

More preferably, R is 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 surface of the metal oxide 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, the interaction between molecules is large, and the intermolecular spacing d between the alkyl groups can be narrowed, and water resistance can be further improved. On the other hand, if the number of carbon atoms is too large, the rate of formation of a monomolecular layer is slow, resulting in poor production efficiency.

In the present invention, R preferably does not contain a halogen atom, particularly a fluorine atom. R preferably does not contain a highly polar functional group (sulfonic acid group, hydroxyl group, carboxylic acid group, amino group, or ammonium group) or a heterocyclic skeleton at one end. A layer formed using a compound that does not contain halogen atoms or these functional groups has high stain removability and high durability.

Among functional groups containing a phosphorus atom, X is at least one selected from a phosphonic acid group, a phosphoric acid group, and a phosphinic acid group, and preferably a phosphonic acid group. Thereby, it is possible to efficiently obtain a sanitary equipment member that has high water resistance and excellent ease of removing contaminants.

The organic phosphonic acid compound represented by the general formula R-X is preferably octadecylphosphonic acid, hexadecylphosphonic acid, dodecylphosphonic acid, decylphosphonic acid, octylphosphonic acid, hexylphosphonic acid, desiloxymethylphosphonic acid, and more preferably Preferred are octadecylphosphonic acid, hexadecylphosphonic acid, dodecylphosphonic acid, and decylphosphonic acid. Even more preferred is octadecylphosphonic acid.

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

In the present invention, the mechanism for improving the ease of stain removal and its persistence is as described above, but in addition to that, the following is also inferred. That is, as shown in FIG. 2(a), when R-X is used, the distance d between the R's constituting the organic layer 10 on the surface of the sanitary equipment member 100 becomes narrower, and the water scale becomes a metal oxide. It is presumed that easy removability is improved because bonding with hydroxyl groups in the layer is suppressed. Here, the "interval d" is the interval between R. Furthermore, since the flexible R bends to cover the base material, it becomes difficult for water molecules to penetrate into the joint between the base material and the compound forming the organic layer. It is presumed that this makes it difficult for the bond between the compound forming the organic layer and the metal oxide to undergo hydrolysis, thereby improving water resistance.

On the other hand, in the techniques disclosed in JP-A-2000-265526 and JP-A-2004-217950, a hydrocarbon group containing a fluorine atom is used. In this case, (i) the molecules are large and cannot be arranged closely due to steric hindrance of the molecules themselves, and (ii) the interaction between molecules is weak, so in the member 200, as shown in FIG. The distance d between the fluorine-containing hydrocarbon groups constituting the organic layer 10 becomes wider. Therefore, it is presumed that unshielded hydroxyl groups remained on the surface of the metal oxide layer and formed chemical bonds with limescale S, making it impossible to obtain sufficient scale removability. Furthermore, since hydrocarbon groups containing fluorine are rigid molecules that do not bend easily, they cannot further cover the gaps between molecules. For this reason, it is presumed that water molecules tend to penetrate into the joint between the base material and the organic layer, resulting in a decrease in water resistance.

The upper limit of the thickness of the organic layer is preferably 50 nm or less, more preferably 20 nm or less, still more preferably 10 nm or less. The lower limit of the thickness of the organic layer is preferably 0.5 nm or more, more preferably 1 nm or more. A suitable range can be determined by appropriately combining these upper and lower limits. Here, "thickness" refers to the length of the organic layer in the Z direction.

As a method for measuring the thickness of the organic layer, any of X-ray photoelectron spectroscopy (XPS), X-ray reflectance spectroscopy (XRR), ellipsometry, and surface-enhanced Raman spectroscopy can be used; In the invention, the thickness of the organic layer is measured by XPS. Even when an organic layer is formed from two or more types of R-X, the thickness measured by XPS is considered the average thickness of the organic layer, and the thickness obtained by the measurements shown below is the thickness of the organic layer. Satoru. In that case, the thickness of the organic layer can be determined by sequential surface composition analysis while exposing the inside of the sample by using a combination of argon ion sputtering or argon gas cluster ion beam (Ar-GCIB) sputtering and XPS measurement. It can be measured by XPS depth profile measurement (see FIGS. 6 and 7 described later). A distribution curve obtained by such XPS depth profile measurement can be created with the vertical axis representing each atomic concentration (unit: at%) and the horizontal axis representing sputtering time. In a distribution curve with sputtering time as the horizontal axis, sputtering time generally correlates with the distance from the surface in the depth direction. As the distance from the surface of the sanitary equipment member (or organic layer) in the Z direction, the distance from the surface of the sanitary equipment member (or organic layer) is determined from the relationship between the sputtering speed and sputtering time adopted during XPS depth profile measurement. can be calculated.

In the case of argon ion sputtering, the measurement point at 0 minutes of sputtering time is taken as the surface (0 nm), and measurement is performed until the distance from the surface to a depth of 20 nm is reached. The carbon concentration in the vicinity of a depth of 20 nm from the surface is defined as the carbon atom concentration in the base material. The carbon atom concentration is measured in the depth direction from the surface, and the maximum depth at which the carbon atom concentration is 1 at% or more higher than the carbon atom concentration of the base material is evaluated as the thickness of the organic layer.

Furthermore, in the case of Ar-GCIB, the thickness of the organic layer is evaluated as follows. First, a standard sample of an organic layer formed using octadecyltrimethoxysilane was prepared on a silicon wafer as a film thickness reference sample, and X-ray reflectance measurement (XRR) (X'pert manufactured by Panalytical Co., Ltd.) was performed. pro) to obtain a reflectance profile. The obtained reflectance profile is fitted to Parratt's multilayer film model and Nevot-Crose's roughness equation using analysis software (X'pert Reflectivity) to obtain the film thickness of the standard sample. Next, Ar-GCIB measurement is performed on the standard sample to obtain the sputtering rate (nm/min) of the SAM. The thickness of the organic layer on the surface of the sanitary equipment member is determined by converting the sputtering time into the distance from the surface of the sanitary equipment member in the Z direction using the obtained sputtering speed. The XRR measurement and analysis conditions and the Ar-GCIB measurement conditions are as follows.

(XRR measurement conditions)
Equipment: X'pert pro (Panalytical)
X-ray source: CuKα
Tube voltage: 45kV
Tube current: 40mA
Incident Beam Optics
Divergence slit: 1/4°
Mask: 10mm
Solar slit: 0.04rad
Anti-scatter slit: 1°
Diffracted Beam Optics
Anti-scatter slit: 5.5mm
Solar slit: 0.04rad
X-ray detector: X'Celerator

Pre Fix Module: Parallel plate Collimator0.27
Incident Beam Optics: Beam Attenuator Type Non
Scan mode: Omega
Incident angle: 0.105-2.935

(XRR analysis conditions)
Set the following initial conditions.
Layer sub: Diamond Si (2.4623g/cm3)
Layer 1: Density Only SiO2 (2.7633g/cm3)
Layer 2 Density Only C (1.6941g/cm3)

(Ar-GCIB measurement conditions)
Equipment: PHI Quantera II (manufactured by ULVAC-PHI)
X-ray conditions: monochromatic AlKα ray, 25W, 15kv
Analysis area: 100mφ
Neutralization gun conditions: 20μA
Io gun condition: 7.00mA
Photoelectron extraction angle: 45°
Time per step: 50ms
Sweep: 10 times Pass energy: 112eV
Measurement interval: 10min
Sputter setting: 2.5kV
Bond energy: Depends on the measured element

Regarding the measurement sample, the measurement point at the sputtering time of 0 minutes is defined as the surface (0 nm), and measurements are made up to the sputtering time of 100 minutes. When measuring the thickness of the organic layer, argon ion sputtering is used to obtain an approximate value semi-quantitatively, and Ar-GCIB, which has high depth resolution, is used to determine the thickness quantitatively. Use.

In the present invention, when measuring the thickness of the organic layer on the surface, the surface of the sanitary equipment member 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 sanitary equipment parts with large surface roughness, such as those that have been subjected to hairline processing or shot blasting, select the part with the highest possible smoothness for measurement.

In the present invention, before confirming in detail that the organic layer is a layer formed using R-X by the method shown below, it is necessary to confirm that the organic layer is formed using a compound having R. It may be confirmed simply by measuring C--C bonds and C--H bonds. C—C bonds and C—H bonds can be confirmed by X-ray photoelectron spectroscopy (XPS), surface-enhanced Raman spectroscopy, and high-sensitivity infrared reflection absorption spectroscopy (IRRAS). When using XPS, a spectrum in the range where the C1s peak appears (278-298 eV) is obtained, and a peak around 284.5 eV derived from the C--C bond and the C--H bond is confirmed. When measuring C--C bonds and C--H bonds, the surface of the sanitary equipment member is cleaned before measurement to sufficiently remove dirt adhering to the surface.

In the present invention, before confirming in detail that the organic layer is a layer formed using RX by the method shown below, it is necessary to confirm that the organic layer is formed using a compound having X. It may be confirmed simply by measuring the bond between a phosphorus atom (P) or a bond between a phosphorus atom (P) and an oxygen atom (O) (PO bond). Phosphorus atoms can be confirmed by determining the phosphorus atom concentration using X-ray photoelectron spectroscopy (XPS). The PO bond can be confirmed by, for example, surface-enhanced Raman spectroscopy, high-sensitivity infrared reflection and absorption spectroscopy, or X-ray photoelectron spectroscopy (XPS). When using XPS, a spectrum in the range where the P2p peak appears (122-142 eV) is obtained, and a peak around 133 eV derived from the PO bond is confirmed.

In the present invention, the fact that the organic layer is a layer formed using RX will be confirmed in detail by the following procedure. First, surface elemental analysis is performed using XPS analysis, and it is confirmed that C, P, and O are detected. 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 a sufficient amount of RX can be recovered from the member. On the other hand, if a sufficient amount of RX 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 RX can be confirmed by detecting the ion intensity of m/z corresponding to ionized RX. 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.

For example, TOF-SIMS5 (manufactured by ION-TOF) is used as a time-of-flight secondary ion mass spectrometry (TOF-SIMS) device. The measurement conditions were: primary ion irradiation: ²⁰⁹ Bi ₃ ⁺⁺ , 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 μm ² , secondary ions to be detected: Positive, Negative, Cycle Time: 110 μs, and number of scans is 16. As a measurement result, a secondary ion mass spectrum (m/z) derived from RX 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.

A time-of-flight tandem mass spectrometer (Q-TOF-MS), for example, Triple TOF 4600 (manufactured by SCIEX), is used as a high-resolution mass spectrometer. For the measurement, for example, the cut out base material is immersed in ethanol, the component (R-X) used to form the organic layer is extracted, unnecessary components are filtered, and then transferred to a vial (about 1 mL). 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.

Confirmation that one end of R consists of C and H and that R is a hydrocarbon consisting of C and H is confirmed using surface-enhanced Raman spectroscopy.

When surface-enhanced Raman spectroscopy is used, it is performed by confirming that one end of R consists of C and H and the Raman shift (cm ^-1 ) derived from the hydrocarbon in which R consists of C and H. The surface-enhanced Raman spectrometer consists of a transmission type surface-enhanced sensor and a confocal micro-Raman spectrometer. As the transmission type surface enhancement sensor, for example, one described in Japanese Patent No. 6179905 is used. For example, NanoFinder 30 (Tokyo Instruments) is used as a confocal micro-Raman spectrometer. The measurement is performed with a transmission type surface-enhanced Raman sensor placed on the surface of the cut-out sanitary equipment member. The measurement conditions are: Nd:YAG laser (532 nm, 1.2 mW), scan time (10 seconds), grating (800 Grooves/mm), and pinhole size (100 μm). Obtain a Raman spectrum as the measurement result. In the Raman spectrum, the horizontal axis is Raman shift (cm ⁻¹ ), and the vertical axis is signal intensity. If one end of R is a methyl group, check the Raman shift (around 2930 cm ^-1 ) derived from the methyl group. If the terminal of R is another hydrocarbon, confirm the corresponding Raman shift. Furthermore, when the hydrocarbon consisting of R and H is an alkyl group (-(CH ₂ ) _n -), confirmation is made by detecting Raman shifts around 2850 cm ^-1 and around 2920 cm ^-1 . In addition, in the case of other hydrocarbon groups, confirm the corresponding Raman shift. A Raman shift signal is considered to have been detected if it is three times or more the average value of the signal intensity at 100 cm ⁻¹ in the lowest signal intensity range in the measurement range.

TOF-SIMS can be used to confirm that R is a hydrocarbon consisting of C and H. When using TOF-SIMS analysis, the peaks detected at every m/z = 14 in the secondary ion mass spectrum obtained under the same analysis conditions as for R-X confirmation are alkyl groups (-(CH ₂ ) _n -) to confirm that it originates from

Confirmation that the organic layer is a monomolecular layer should be performed based on the thickness of the organic layer obtained by the above method and the molecular structure of the compound represented by the general formula RX identified by the above method. I can do it. First, the molecular length of the compound represented by the general formula RX is estimated based on the identified molecular structure. If the thickness of the obtained organic layer is less than twice the estimated molecular length of the compound, it is considered to be a monomolecular layer. Note that the thickness of the organic layer is the average value of the thicknesses obtained by measuring at three different points. In addition, when the organic layer is formed from two or more types of compounds represented by the general formula RX, the thickness of the obtained organic layer is less than twice the longest molecular length of the estimated compound. If so, it is considered a monolayer.

Confirmation that the organic layer is a SAM can be performed by confirming that the organic layer forms a dense layer in addition to confirming that the organic layer is a monomolecular layer as described above. Confirmation that the organic layer forms a dense layer can be made by checking the phosphorus atom concentration on the surface described above. That is, if the phosphorus atom concentration is 1.0 at% or more, it can be said that the organic layer forms a dense layer.

In the organic layer and the metal oxide layer, as shown in FIG. 2(b), the metal atom (M) derived from the metal oxide layer and the phosphorus atom (P) derived from the compound RX are oxygen atoms (O). It is thought that they are bonded through (M-O-P bond). The M-O-P bond can be used, for example, in time-of-flight secondary ion mass spectrometry (TOF-SIMS), surface-enhanced Raman spectroscopy, infrared reflection and absorption spectroscopy, infrared absorption spectroscopy, and X-ray photoelectron spectroscopy (XPS). However, in the present invention, confirmation is performed by using both time-of-flight secondary ion mass spectrometry (TOF-SIMS) and surface-enhanced Raman spectroscopy. When X is a phosphonic acid group, a maximum of three M--O--P bonds can be formed per X. By fixing one X to the metal oxide with multiple M--O--P bonds, the water resistance and abrasion resistance of the organic layer are improved.

In the present invention, the M--O--P bond is confirmed by the following procedure. First, surface elemental analysis is performed using XPS analysis, and it is confirmed that C, P, and O are detected. Next, a time-of-flight secondary ion mass spectrometer (TOF-SIMS), for example, TOF-SIMS5 (manufactured by ION-TOF) is used. The measurement conditions were: primary ion irradiation: ²⁰⁹ Bi ₃ ⁺⁺ , 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 μm ² , secondary ions to be detected: Positive, Negative, Cycle Time: 110 μs, and number of scans is 16. As the measurement results, a secondary ion mass spectrum derived from the combination of R-X and metal oxide element M (R-X-M) and a secondary ion mass spectrum (m/z) derived from M-O-P. Confirm by obtaining each. 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.

Next, the Raman shift (cm ^-1 ) derived from the M--O--P bond is confirmed by surface-enhanced Raman spectroscopy. The surface-enhanced Raman spectrometer consists of a transmission type surface-enhanced sensor and a confocal micro-Raman spectrometer. As the transmission type surface enhancement sensor, for example, one described in Japanese Patent No. 6179905 is used. For example, NanoFinder 30 (Tokyo Instruments) is used as a confocal micro-Raman spectrometer. The measurement is performed with a transmission type surface-enhanced Raman sensor placed on the surface of the cut-out sanitary equipment member. The measurement conditions are: Nd:YAG laser (532 nm, 1.2 mW), scan time (10 seconds), grating (800 Grooves/mm), and pinhole size (100 μm). Obtain a Raman spectrum as the measurement result. In the Raman spectrum, the horizontal axis is Raman shift (cm ⁻¹ ), and the vertical axis is signal intensity. The signal derived from the M--O--P bond can be assigned from the Raman spectrum in which the bonding state of the M--O--P bond is estimated using a first-principles calculation software package: Material Studio. Regarding structural optimization, the calculation conditions for first-principles calculations include, for example, the software used (CASTEP), functional (LDA/CA-PZ), cutoff (830eV), K point (2 * 2 * 2), This is performed using potential (Norn-conserving), Density mixing (0.05), spin (ON), and Metal (OFF). In addition, for Raman spectrum calculation, for example, the software used (CASTEP), functional (LDA/CA-PZ), cutoff (830eV), K point (1 * 1 * 1), pseudopotential (Norn-conserving), Density Performed by mixing (All Bands/EDFT), spin (OFF), and Metal (OFF). For example, in the case of a phosphonic acid group, the bonding state of M-O-P is one M-O-P bond per phosphonic acid group, and one M-O-P bond per phosphonic acid group. Two states, three M-O-P bonds per phosphonic acid group, are possible. It is confirmed that the sanitary equipment member of the present invention includes at least one of the bonded states. When assigning a Raman spectrum obtained from surface-enhanced Raman spectroscopy to a Raman spectrum obtained by first-principles calculation, it is necessary to identify two or more characteristic Raman shifts for each M-O-P bond state. Confirm that it is being followed. Here, the Raman shifts are said to match based on first-principles calculations in the range of ±2.5 cm ^-1 (5 cm ^-1 ) of the Raman shift value considered to originate from the M-O-P bond to be compared. , meaning that signals are detected in both surface-enhanced Raman spectroscopy.

In the sanitary equipment member of the present invention, the phosphorus atom concentration on the surface is preferably 1.0 at% or more and less than 10 at%. By setting the phosphorus atom concentration within this range, it is shown that the organic layer is dense. This makes it possible to obtain a sanitary equipment member 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.

The phosphorus atom concentration on the surface of the sanitary equipment member of the present invention can be determined by X-ray photoelectron spectroscopy (XPS). As the measurement conditions, wide scan analysis (also referred to as survey analysis) is performed using Condition 1.

(Condition 1)
X-ray conditions: Monochromatic AlKα rays (output 25W)
Photoelectron extraction angle: 45°
Analysis area: 100μmφ
Operation range: 15.5-1100eV

PHI Quantera II (manufactured by ULVAC-PHI) can be used as the XPS device. X-ray conditions (monochromatic AlKα ray, 25W, 15kv), analysis area: 100μmφ, neutralization gun conditions (Emission: 20μA), ion gun conditions (Emission: 7.00mA), photoelectron extraction angle (45°), Time per A spectrum is obtained by wide scan analysis under the following conditions: step (50 ms), sweep (10 times), pass energy (280 eV), and scan range (15.5 to 1100 eV). The spectrum is measured in a form that includes carbon atoms, phosphorus atoms, etc. detected from the organic layer, and atoms detected from the base material, such as chromium atoms and oxygen atoms in the case of a Cr plating base material. The concentration of the detected atoms can be calculated from the obtained spectrum using, for example, data analysis software PHI MultiPuk (manufactured by ULVAC-PHI). The obtained spectrum was charge-corrected by setting the C1s peak at 284.5 eV, and then the background was removed using the Shirely method for peaks based on the measured electron orbits of each atom, and then the peak area intensity was calculated and data analysis was performed. The phosphorus atom concentration (hereinafter referred to as C _P ) can be calculated by performing an analysis process of dividing by a sensitivity coefficient specific to the device that is preset in the software. In addition, the carbon atom concentration (hereinafter referred to as C _C ), the oxygen atom concentration (hereinafter referred to as C _O ), and the metal atom concentration (hereinafter referred to as C _M ) can be similarly obtained. The concentration calculation uses the peak areas of the P2p peak for phosphorus, the C1s peak for carbon, the O1s peak for oxygen, the Cr2p3 peak for chromium, the Ti2p peak for titanium, and the Zr3d peak for zirconium.

In the present invention, when performing a surface analysis, a portion of a sanitary equipment member with a relatively large radius of curvature is selected and cut into a size that can be analyzed, and the sample is used as a measurement sample. When cutting, cover the area to be analyzed and evaluated with a film to prevent surface damage. Before measurement, clean the surface of the sanitary equipment member and thoroughly remove dirt adhering to the surface. For example, after sponge sliding cleaning using a neutral detergent, rinsing is thoroughly performed using ultrapure water. In the present invention, elements detected by XPS analysis are carbon, oxygen, phosphorus, and atoms originating from the base material and metal oxide layer. Atoms derived from the base material and the metal oxide layer may include nitrogen and the like in addition to the metal atoms forming the base material and the metal oxide layer. If the base material includes chromium plating, carbon, oxygen, phosphorus, and chromium are detected. If any other element is detected, it is considered to be a contaminant attached to the surface of the metal oxide layer. When a high concentration of atoms derived from a pollutant is detected (when the concentration of atoms derived from a pollutant exceeds 3 at%), it is regarded as an abnormal value. If an abnormal value is obtained, the atomic concentration is calculated by excluding the abnormal value. If there are many abnormal values, clean the surface of the sanitary equipment member again and repeat the measurement. In addition, if the sanitary equipment member is a metal member with a large surface roughness, such as a hairline finish on the surface, select a part with the highest possible smoothness for measurement.

In the sanitary equipment member of the present invention, the carbon atom concentration on the surface is preferably 35 at% or more, more preferably 40 at% or more, still more preferably 43 at% or more, and most preferably 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.

The carbon atom concentration (hereinafter referred to as C _C ) on the surface of the sanitary equipment member of the present invention can be determined by X-ray photoelectron spectroscopy (XPS) similarly to the measurement of the phosphorus atom concentration. As the measurement conditions, the above-mentioned Condition 1 is used to perform wide scan analysis.

The sanitary equipment member of the present invention includes a base material 70 at least whose surface contains a metal element, and a metal oxide layer 20 formed on the base material 70. The metal oxide layer 20 is a layer containing at least the metal element and oxygen element. The metal oxide layer 20 contains the metal element in an oxidized state. There may not be a clear boundary between the base material 70 and the metal oxide layer 20. The metal element is one in which a pure metal or an alloy containing the element can form a passive film, and in the present invention, it is at least one selected from the group consisting of Cr, Zr, and Ti. By setting the metal element within such a range, a stable passive layer can be formed on the surface of the base material. The stable passive layer herein refers to a layer containing a metal oxide and having sufficient water resistance. More preferably, the metal element is Cr or Zr. By setting the metal element within such a range, the metal oxide layer on the surface of the base material becomes a more stable passive layer, and water resistance can be further improved. The metal element can be determined by X-ray photoelectron spectroscopy (XPS).

In addition to the above-mentioned elements, Ni and Al are also known as metal elements that can form a passive film. However, it has been found that when a metal oxide layer consisting of Ni or Al and an oxygen element is applied to sanitary equipment components, there is a tendency for the ability to remove limescale to deteriorate and for the appearance to deteriorate due to the occurrence of widely distributed spots. Ta. For this reason, it is not preferable to apply it to sanitary equipment members where aesthetic appearance is particularly important to the user. The decrease in scale removal performance and the occurrence of poor appearance are thought to be due to water entering the organic layer and deterioration of the metal oxide layer due to long-term use of sanitary equipment members.

The metal oxide layer 20 is a passive layer formed on the surface of the base material 70 or a layer artificially formed on the surface of the base material 70, but it has durability such as water resistance and abrasion resistance. A passive layer is preferable since an excellent organic layer can be obtained. Examples of the means for artificially forming it include a sol-gel method, a chemical vapor deposition method (CVD), and a physical vapor deposition method (PVD).

Further, the base material 70 may be provided with a region 70b. The region 70b is, for example, a layer containing metal formed by metal plating or physical vapor deposition (PVD). The region 70b 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.). The base material 70 includes a support material 70c. The material of the support member 70c may be metal, resin, ceramic, earthenware, or glass. Region 70b may be formed directly on support 70c, or may include different layers between region 70b and support 70c. Examples of the base material 70 on which the region 70b is provided include a metal-plated product in which the region 70b is provided on a support material 70c made of brass or resin by metal plating. On the other hand, examples of the base material 70 in which the region 70b is not provided include a metal molded product such as stainless steel (SUS). The surface properties of the base material 70 are not particularly limited, and the base material 70 can be applied to a glossy mirror surface, a matte surface such as a satin surface, a hairline surface, and the like.

In the sanitary equipment member of the present invention, the oxygen atom/metal atom concentration ratio (O/M ratio) on the surface is preferably greater than 1.7, more preferably 1.8 or more. By setting the O/M ratio in such a range, the sanitary equipment member of the present invention can strongly bond a dense organic layer to a metal oxide layer with a relatively high degree of oxidation. Water resistance and abrasion resistance can be increased.

The O/M ratio (R _O/M ) can be calculated by formula (A) using the above C _O and C _M obtained by XPS analysis.

R _O/M = C _O /C _M ... Formula (A)

Note that when calculating R _O/M when R contains an ether group or a carbonyl group, Co is the sum of the oxygen atom concentration C _O' originating from RX and the oxygen atom concentration originating from the metal base material. It can be calculated based on equation (B), keeping in mind that

How to determine C _O' : From the molecular structure specified by TOF-SIMS or HR-MS, from the ratio of oxygen atoms to carbon atoms contained in R, and by relative comparison with C _C , the concentration of oxygen atoms contained in R C _O Estimate _´ .

R _O/M = (C _O - C _O' )/C _M ... Formula (B)

In the sanitary equipment member of the present invention, the oxidation state of the metal element in the metal oxide layer can be confirmed by XPS. Narrow scan analysis is performed using condition 2 as the measurement condition.

(Condition 2)
X-ray conditions: Monochromatic AlKα rays (output 25W)
Photoelectron extraction angle: 45°
Analysis area: 100μmφ
Operating range: varies by element (see next paragraph)

PHI Quantera II (manufactured by ULVAC-PHI) can be used as the XPS device. X-ray conditions (monochromatic AlKα ray, 25W, 15kv), analysis area: 100μmφ, neutralization gun conditions (Emission: 20μA), ion gun conditions (Emission: 7.00mA), photoelectron extraction angle (45°), Time per A spectrum of each metal element peak is obtained by performing narrow scan analysis under the conditions of step (50 ms), sweep (10 times), and pass energy (112 eV). For example, when the metal element contained in the metal oxide layer is Cr, a spectrum of the Cr2p3 peak is obtained by narrow scan analysis in the range of 570 to 590 eV. Chromium (Cr) in an oxidized state can be confirmed by the presence of a peak around 577 eV. Titanium (Ti) in an oxidized state can be confirmed by the presence of a peak around 469 eV in the Ti2p peak spectrum. Zirconium (Zr) in an oxidized state can be confirmed by the presence of a peak around 182 eV among the Zr3d peaks.

The sanitary equipment member of the present invention preferably has a water droplet contact angle on its surface of 90° or more, more preferably 100° or more. The water droplet contact angle means a static contact angle, and is determined by dropping a 2 μl water droplet onto a substrate and photographing the water droplet 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.

In the present invention, "sanitary equipment" refers to water supply and drainage equipment of a building or indoor fixtures, preferably indoor fixtures. Preferably, it is used in an environment where it may be exposed to water.

In the present invention, an environment that can be exposed to water may be any place that uses water, and includes places that use water such as residences, parks, commercial facilities, offices, and other public facilities. Preferably, a bathroom, a toilet space, a restroom, a washroom, a kitchen, etc. can be mentioned.

In the present invention, indoor fixtures are those that are used in public facilities such as residences and commercial facilities and are touched by people, preferably in bathrooms, toilet spaces, restrooms, washrooms, or kitchens. This is the equipment used. Examples of sanitary equipment members used as indoor fixtures of the present invention include products that are plated or PVD coated. 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 sanitary equipment components of the present invention include faucets, faucet fittings, drain fittings, water stop fittings, wash 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 sanitary equipment member of the present invention can be suitably used as a faucet or a faucet that spouts hot water.

Sanitary equipment members with a densely formed organic layer, that is, sanitary equipment members whose surface has a phosphorus atom concentration of 1.0 at% or more, and sanitary equipment members whose organic layer is SAM, are exposed to hot water. However, since the organic layer has excellent durability, it can be suitably used as a faucet for discharging hot water.

The sanitary equipment member of the present invention preferably includes a step of preparing a base material, a step of increasing the degree of oxidation on the surface of the base material, and a general formula R-X (R is a hydrocarbon group, X is a phosphonic acid group, It can be produced by a method including a step of applying a compound represented by at least one selected from acid groups and phosphinic acid groups. A specific example is shown below.

In the present invention, after cleaning a base material containing a metal element on the surface, an organic layer is formed by contacting the base material with a solution containing a compound represented by the general formula RX. It is preferable that the base material is previously subjected to a treatment to increase the degree of oxidation of its surface, preferably passivation treatment, to form a sufficient metal oxide layer. For the passivation treatment, in addition to known methods, ultraviolet irradiation, ozone exposure, wet treatment, and combinations thereof can be suitably used. The method of bringing the solution into contact with the base material is not particularly limited, but examples include methods such as a dipping method in which the base material is immersed in the solution, a coating method by spraying or wiping, and a misting method in which the base material is brought into contact with a mist of the solution. It will be done. Preferably, the organic layer is formed by a dipping method in which the substrate is immersed in a solution. The temperature and immersion time when immersing the substrate in the solution vary depending on the type of substrate and organic phosphonic acid compound, but are generally 0° C. or higher and 60° C. or lower, and 1 minute or more and 48 hours or less. In order to form a dense organic layer, it is preferable to lengthen the immersion time. It is preferable to heat the base material after forming the organic layer on the base material. Specifically, the substrate is heated to a temperature of 40° C. or higher and 250° C. or lower, preferably 60° C. or higher and 200° C. or lower. This promotes the bonding between the components constituting the organic layer and the base material, increases the number of M-O-P bonds per phosphonic acid group, and improves the water resistance and abrasion resistance of the organic layer. improves.

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

1. Sample preparation 1-1. Base material As a base material, a plate of brass plated with nickel chrome (samples 1 to 7, 12 to 14, 16 to 18, and 20), a plate of plate of nickel chrome plated to brass, and a surface containing metal by physical vapor deposition (PVD). A stainless steel plate (SUS304) (sample 11), a brass plate (sample 19), and an aluminum plate (sample 21) were used. In order to remove dirt from the surface of the substrate, ultrasonic cleaning was performed using an aqueous solution containing a neutral detergent, and after cleaning, the substrate was thoroughly rinsed with running water. Furthermore, in order to remove the neutral detergent from the base material, it was subjected to ultrasonic cleaning using ion-exchanged water, and then water was removed using an air duster.

Furthermore, a faucet fitting made of brass plated with nickel chrome (product number: TENA40A, manufactured by TOTO Corporation; sample 22) was used. Dirt on the surface of the substrate was removed in the same manner as above. Samples 1 to 18, 20, and 22 have a metal oxide layer consisting of a passive layer on the surface of the base material. Sample 20 has no metal oxide layer.

1-2. Pretreatment (Samples 1, 5-12, 17, 19, and 21)
The base material was introduced into a photosurface treatment device (PL21-200 (S), manufactured by Sen Engineering) and subjected to UV ozone treatment for a predetermined period of time.
(Sample 2)
The base material was introduced into a plasma CVD apparatus (PBII-C600, manufactured by Kurita Industries) and subjected to argon sputtering treatment for a predetermined time under a vacuum condition of about 1 Pa. Subsequently, oxygen was introduced into the apparatus to perform oxygen plasma treatment.
(Sample 3 and Sample 22)
After the base material was immersed in an aqueous sodium hydroxide solution for a predetermined time, it was thoroughly rinsed with ion-exchanged water.
(Sample 4)
After the base material was immersed in dilute sulfuric acid for a predetermined time, it was thoroughly rinsed with ion-exchanged water.
(Sample 13)
After scrubbing the base material with an abrasive made of cerium oxide, it was thoroughly rinsed with ion-exchanged water.
(Sample 14)
After scrubbing the base material with a weak alkaline abrasive (product name: Kiraria, manufactured by TOTO), it was thoroughly rinsed with ion-exchanged water.
(Sample 18)
After polishing the base material with a diamond paste abrasive (particle size: 1 μm), it was thoroughly rinsed with ion-exchanged water.
(Samples 15, 16 and 20)
No pretreatment of the substrate was performed.

1-3. Formation of organic layer (samples 1-5 and 8-16, 18, 19, 21, and 22)
As a treatment agent for forming the organic layer, a solution in which octadecylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd., product code O0371) was dissolved in ethanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., Wako 1st grade) was used. The base material was immersed in the treatment agent for a predetermined time and washed by washing with ethanol. The immersion time was 1 minute or more for Samples 1 to 5, 8 to 16, 19, 21, and 22, and 10 seconds or less for Sample 18. Thereafter, it was dried in a dryer at 120° C. for 10 minutes to form an organic layer on the surface of the base material.
(Sample 6)
As a processing agent for forming the organic layer, a solution in which dodecylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd., product code D4809) was dissolved in ethanol was used. The immersion time was 1 minute or more. Thereafter, it was dried in a dryer at 120° C. for 10 minutes to form an organic layer on the surface of the base material.
(Sample 7)
As a treatment agent for forming the organic layer, a solution in which octadecylphosphonic acid and phenylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd., product code P0204) were dissolved in ethanol at a weight ratio of 1:1 was used. The immersion time was 1 minute or more. Thereafter, it was dried in a dryer at 120° C. for 10 minutes to form an organic layer on the surface of the base material.
(Sample 17)
As a treatment agent for forming an organic layer with a hydrocarbon group containing a fluorine atom, (1H,1H,2H,2H-heptadecafluorodecyl)phosphonic acid (manufactured by Tokyo Kasei Kogyo, product code H1459) was dissolved in ethanol. A solution was used. The immersion time was 1 minute or more. Thereafter, it was dried in a dryer at 120° C. for 10 minutes to form an organic layer containing fluorine atoms on the surface of the base material.
(Sample 20)
No organic layer was allowed to form.

Table 1 shows an overview of the prepared samples.

2. Analysis/Evaluation Method The following analyzes and evaluations were conducted for each sample prepared above. Regarding sample 22, a sample cut into a size of about 10 mm x about 10 mm was used as a measurement sample. The measurement sample was cut out from the side of the spout, which is a portion with a relatively large radius of curvature. During cutting, the area to be analyzed and evaluated was covered with a film to prevent surface damage.

2-1. Water droplet 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 2 as water contact angle/initial.

2-2. Removal of water scale stains Water scale was formed on the surface of each sample by dropping 20 μl of tap water onto the surface of each sample and leaving it for 24 hours. Samples with limescale formed were evaluated according to the following procedure.
(i) Using a dry cloth, the surface of the sample was slid back and forth 10 times while applying a light load (50 gf/cm ² ).
(ii) Using a dry cloth, the surface of the sample was slid back and forth 10 times while applying a heavy load (100 gf/cm ² ).
Those that could be removed in step (i) are marked as "◎", those that could be removed in step (ii) as "○", and those that could not be removed as "×", and are summarized in Table 1.
Note that whether or not scale could be removed was determined by rinsing the surface of the sample with running water, removing water with an air duster, and then visually determining whether scale remained on the surface of the sample. The evaluation results are shown in Table 2 as scale removal performance/initial stage.

2-3. Water Resistance Test After the surface of each sample was immersed in 70° C. warm water for a predetermined time, the surface of the sample was rinsed with running water, and moisture was removed using an air duster. After the water resistance test, each sample was evaluated for its ability to remove limescale stains. Those that could be removed by method 2-2 (ii) after 2 hours of immersion were marked as "○", and those that could not be removed were marked as "x". Furthermore, those that could be removed by method 2-2 (ii) after 48 hours of immersion were marked as "○~◎", and those that could be removed by method (ii) after 120 hours of immersion were marked as "◎". . The evaluation results are shown in Table 2 after the scale removal and water resistance tests.

2-4. Removal of sebum stains The sebum stain solutions listed in Table 3 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 2 as sebum stain removability/initial stage.

2-5. Abrasion Resistance Test The surface of each sample was slid 3000 times using a melamine sponge while applying a load (200 gf/cm ² ) to the sample surface with the melamine sponge soaked in water. After sliding, the sample surface was rinsed with running water and moisture was removed with an air duster. After the abrasion test, each sample was evaluated for water droplet contact angle measurement and sebum stain removability. The evaluation results are shown in Table 2 after the water contact angle/abrasion resistance test and after the sebum stain removability/abrasion resistance test.

2-6. Measurement of each atomic concentration Each atomic concentration on the surface of each sample was determined by X-ray photoelectron spectroscopy (XPS). Before measurement, the sample was scrubbed with a urethane sponge using a neutral detergent, and then thoroughly rinsed with ultrapure water. PHI Quantera II (manufactured by ULVAC-PHI) was used as the XPS device. X-ray conditions (monochromatic AlKα ray, 25W, 15kv), analysis area: 100μmφ, neutralization gun conditions (Emission: 20μA), ion gun conditions (Emission: 7.00mA), photoelectron extraction angle (45°), Time per A spectrum was obtained by wide scan analysis under the following conditions: step (50 ms), sweep (10 times), pass energy (280 eV), and scan range (15.5 to 1100 eV). The concentration of the detected atoms was calculated from the obtained spectrum using data analysis software PHI MultiPuk (manufactured by ULVAC-PHI). The obtained spectrum was charge-corrected by setting the C1s peak at 284.5 eV, and then the background was removed using the Shirely method for peaks based on the measured electron orbits of each atom, and then the peak area intensity was calculated and data analysis was performed. An analysis process is performed to divide by the device-specific sensitivity coefficient preset in the software, and the phosphorus atomic concentration (hereinafter, _CP ), oxygen atomic concentration (hereinafter, _CO ), metal atomic concentration (hereinafter, _CM ), and the carbon atom concentration (hereinafter referred to as C _C ). For concentration calculation, the peak areas of the P2p peak for phosphorus, the C1s peak for carbon, the O1s peak for oxygen, the Cr2p3 peak for chromium, the Ti2p peak for titanium, and the Zr3d peak for zirconium were used. The value of each concentration was the average value of measurements taken at three different locations. However, if an abnormal value appeared among the three locations, the average value was calculated by excluding the abnormal value. Table 2 shows the concentrations of phosphorus atoms, oxygen atoms, metal atoms, and carbon atoms obtained.

2-7. Calculation of R _O/M Using C _O and C _M obtained by XPS analysis, R _O/M was calculated according to formula (A). The obtained R _O/M values are shown in Table 2.

R _O/M = C _O /C _M ... Formula (A)

2-9. C1s spectrum Before measurement, the sponge was rubbed with a neutral detergent and rinsed thoroughly with ultrapure water. PHI Quantera II (manufactured by ULVAC-PHI) was used as the XPS device. X-ray conditions (monochromatic AlKα ray, 25W, 15kv), analysis area: 100μmφ, neutralization gun conditions (Emission: 20μA), ion gun conditions (Emission: 7.00mA), photoelectron extraction angle (45°), Time per A C1s spectrum was obtained by measuring under the following conditions: step (50 ms), sweep (10 times), pass energy (112 eV), and scan range (278 to 298 eV). The C1s spectrum of sample 3 is shown in FIG.

2-10. P2p spectrum Before measurement, the sponge was rubbed with a neutral detergent and rinsed thoroughly with ultrapure water. PHI Quantera II (manufactured by ULVAC-PHI) was used as the XPS device. X-ray conditions (monochromatic AlKα ray, 25W, 15kv), analysis area: 100μmφ, neutralization gun conditions (Emission: 20μA), ion gun conditions (Emission: 7.00mA), photoelectron extraction angle (45°), Time per A P2p spectrum was obtained by measuring under the following conditions: step (50 ms), sweep (10 times), pass energy (112 eV), and scan range (122 to 142 eV). The P2p spectrum of sample 3 is shown in FIG.

2-11. Confirmation of Metal Elements in Oxide Layer For Samples 1 to 18 and 22, it was confirmed by X-ray photoelectron spectroscopy (XPS) that the metal elements were in an oxide state. Before measurement, the sponge was rubbed with a neutral detergent and rinsed thoroughly with ultrapure water. PHI Quantera II (manufactured by ULVAC-PHI) can be used as the XPS device. X-ray conditions (monochromatic AlKα ray, 25W, 15kv), analysis area: 100μmφ, neutralization gun conditions (Emission: 20μA), ion gun conditions (Emission: 7.00mA), photoelectron extraction angle (45°), Time per A spectrum of each metal element peak was obtained by narrow scan analysis under the conditions of step (50 ms), sweep (10 times), and pass energy (112 eV). The range of narrow scan analysis is the range of Cr2p3 peak for samples 1-7, 11-14, 16-18, and 22, the range of Ti2p peak for samples 8, 9, and 15, and the range of Zr3d peak for sample 10. The background of the obtained peaks was removed using the Shirely method, and it was confirmed that all samples contained metal elements in an oxidized state.

2-12. Organic layer thickness evaluation 1
The thickness of the organic layer was evaluated by XPS depth profile measurement. XPS measurement was performed under the same conditions as 2-9. The argon ion sputtering conditions were such that the sputtering rate was 1 nm/min. Using this sputtering speed, the sputtering time was converted into the distance from the sample surface in the Z direction. The measurement point at the sputtering time of 0 minutes was taken as the surface (0 nm), and measurements were made to a distance of 20 nm from the surface. The carbon concentration in the vicinity of a depth of 20 nm from the surface was defined as the carbon atom concentration in the base material. The carbon atom concentration was measured in the depth direction from the sample surface, and the maximum depth at which the carbon atom concentration was 1 at% or more higher than the carbon atom concentration of the base material was evaluated as the thickness of the organic layer. In all samples, the thickness of the organic layer was 5 nm or less. As a measurement example, the XPS depth profile of Sample 3 is shown in FIG.

2-13. Organic layer thickness evaluation 2
The thickness of the organic layer was evaluated by XPS depth profile measurement using an argon gas cluster ion beam (Ar-GCIB). XPS measurement was performed under the same conditions as 2-9. The Arcon sputtering conditions were as follows: ion source: Ar2500+, acceleration voltage: 2.5 kV, sample voltage: 100 nA, sputter area: 2 mm x 2 mm, charge neutralization condition: 1.1 V, and ion gun: 7 V. The sputtering rate was determined by Ar-GCIB measurement of octadecyltrimethoxysilane (1.6 nm), which was formed as a standard sample on a silicon wafer whose film thickness was previously measured by X-ray reflectance method (XRR). The value (0.032 nm/min) was used.

The film thickness of the standard sample is measured by X-ray reflectance measurement (XRR) (X'pert pro manufactured by Panalytical) to obtain a reflectance profile. The obtained reflectance profile was fitted to Parratt's multilayer film model and Nevot-Crose's roughness equation using analysis software (X'pert Reflectivity) to obtain the film thickness of the standard sample. Next, Ar-GCIB measurement was performed on the standard sample, and the sputtering rate (0.029 nm/min) of the organic layer was obtained. The thickness of the organic layer on the sample (organic layer) was determined by converting the sputtering time into the distance from the sample surface in the Z direction using the obtained sputtering speed. The XRR measurement and analysis conditions and the Ar-GCIB measurement conditions are as follows.

(XRR measurement conditions)
Equipment: X'pert pro (Panalytical)
X-ray source: CuKα
Tube voltage: 45kV
Tube current: 40mA
Incident Beam Optics
Divergence slit: 1/4°
Mask: 10mm
Solar slit: 0.04rad
Anti-scatter slit: 1°
Diffracted Beam Optics
Anti-scatter slit: 5.5mm
Solar slit: 0.04rad
X-ray detector: X'Celerator

Pre Fix Module: Parallel plate Collimator0.27
Incident Beam Optics: Beam Attenuator Type Non
Scan mode: Omega
Incident angle: 0.105-2.935

(XRR analysis conditions)
Set the following initial conditions.
Layer sub: Diamond Si (2.4623g/cm ³ )
Layer 1: Density Only SiO ₂ (2.7633g/cm ³ )
Layer 2 Density Only C (1.6941g/cm ³ )

(Ar-GCIB measurement conditions)
Equipment: PHI Quantera II (manufactured by ULVAC-PHI)
X-ray conditions: monochromatic AlKα ray, 25W, 15kv
Analysis area: 100mφ
Neutralization gun conditions: 20μA
Io gun condition: 7.00mA
Photoelectron extraction angle: 45°
Time per step: 50ms
Sweep: 10 times Pass energy: 112eV
Measurement interval: 10min
Sputter setting: 2.5kV
Binding energy: C1s (278-298eV)

Using this sputtering speed, the sputtering time was converted into the distance from the sample surface in the Z direction. The carbon atom concentration was measured in the depth direction from the surface of the sample by setting the measurement point at the sputtering time of 0 minutes as the surface (0 nm) and measuring until the sputtering time of 100 minutes. A depth profile is plotted for each depth, with the horizontal axis representing the depth converted from the sputtering speed (nm) and the vertical axis representing the surface carbon (C1s) concentration as 100%, and the horizontal axis representing the inflection point of the depth profile curve. The thickness of the organic layer was calculated from The film thickness was the average value measured at three different locations. However, if an abnormal value appeared among the three locations, the average value was calculated by excluding the abnormal value. The results are shown in Table 2. As a measurement example, the XPS AR-GCIB depth profile of Sample 3 is shown in FIG. The film thickness obtained from the inflection point of the depth profile was 2.0 nm.

2-14. Water Resistance Test 2_Evaluation of Appearance After immersing samples 1 to 22 in warm water at 90° C. for 1 hour, the samples were taken out and the hot water adhering to the samples 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 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 2.

(R-X confirmation)
RX was confirmed using TOF-SIMS and ESI-TOF-MS/MS.

(R-X confirmation by TOF-SIMS)
TOF-SIMS measurement conditions are: primary ion irradiation: ²⁰⁹ Bi ₃ ⁺⁺ , primary ion acceleration voltage 25 kV, pulse width 10.5 or 7.8 ns, with bunching, no charge neutralization, post-acceleration 9.5 kV, measurement range (Area): approximately 500×500 μm ² , Secondary ions to be detected: Positive, Negative, Cycle Time: 110 μs, Number of scans was 16.

For samples 1-5, 7-16, 18, 19, 21, and 22 using octadecylphosphonic acid (C ₁₈ H ₃₉ O ₃ P) as the treatment agent, m/z = 335 (C _{18 It} was confirmed that a peak at m/ _z =333 (C ₁₈ H ₃₈ O ₃ P ⁻ ) was detected in ^the negative mode.

For sample 6 using dodecylphosphonic acid (C ₁₂ H ₂₇ O ₃ P) as a processing agent, m/z = 251 (C ₁₂ H ₂₈ O ₃ P ⁺ ) in the positive mode, and m/z = 251 (C 12 H 28 O 3 P + ) in the negative mode. It was confirmed that the peaks of 249 (C ₁₂ H ₂₆ O ₃ P ⁻ ) were detected.

Regarding sample 7, in which octadecylphosphonic acid (C ₁₈ H ₃₉ O ₃ P) and phenylphosphonic acid (C ₆ H ₇ O ₃ P) were used as a treatment agent at a weight ratio of 1:1, regarding octadecylphosphonic acid It was confirmed that the same peak as Sample 1 was detected. Regarding phenylphosphonic acid, a peak of m/z = 159 (C ₆ H ₈ 〇 ₃ P ⁺ ) was detected in the positive mode, and a peak of m/z = 157 (C ₆ H ₆ 〇 ₃ P ⁻ ) was detected in the negative mode. I was sure that.

(ESI-TOF-MS/MS)
Triple TOF 4600 (manufactured by SCIEX) was used for ESI-TOF-MS/MS measurement. For measurement, the cut out base material is immersed in ethanol, each treatment agent used to form the organic layer is extracted, unnecessary components are filtered, and the sample is transferred to a vial (approximately 1 mL) before measurement. The measurement conditions are: ion source: ESI/Duo Spray Ion Source, ion mode (Positive/Negative), IS voltage (4500/-4500V), source temperature (600°C), DP (100V), CE (40V/-40V) MS/MS measurements were performed.

For samples 1-5, 7-16, 18, 19, 21, and 22 using octadecylphosphonic acid (C ₁₈ H ₃₉ O ₃ P) as the treatment agent, m/z = 335.317 (C ₁₈ H ₄₀ O ₃ P ⁺ ), m/z = 333.214 (C ₁₈ H ₃₈ O ₃ P ⁻ ), m/z = 78.952 (C ₁₈ H ₃₈ O ₃ P in negative mode). It was confirmed that the peaks of ^- fragment ions PO ₃ ^- ) were detected. FIG. 8 shows the spectrum obtained by Q-TOF-MS/MS analysis of Sample 3.

For sample 6 using dodecylphosphonic acid (C ₁₂ H ₂₇ O ₃ P) as a processing agent, m/z = 251.210 (C ₁₂ H ₂₇ O ₃ P ⁺ ) in the positive mode of MS/MS analysis, negative In the mode, the peaks of m/z=249.138 (C ₁₂ H ₂₆ O ₃ P ⁻ ) and m/z=78.954 (fragment ion PO ₃ ⁻ of C ₁₂ H ₂₇ O ₃ P ⁻ ) are detected, respectively. It was confirmed.

Regarding sample 7, in which octadecylphosphonic acid (C ₁₈ H ₃₉ O ₃ P) and phenylphosphonic acid (C ₆ H ₇ O ₃ P) were used as a treatment agent at a weight ratio of 1:1, regarding octadecylphosphonic acid It was confirmed that the same peak as Sample 1 was detected. For phenylphosphonic acid, m/z = 159.036 (C ₆ H ₈ O ₃ P ⁺ ) in the positive mode of MS/MS analysis, m/z = 156.985 (C ₆ H ₆ 〇 ₃ P + ) in the negative mode. It was confirmed that the peaks at m/z=79.061 (fragment ion of C ₆ ^H ₆ ³⁺ ) were detected in the positive mode of MS/MS analysis.

(Confirmation that one end of R (the end that is not bonded to X) consists of C and H)
Surface-enhanced Raman spectroscopy was used to confirm that one end of R consists of C and H and that R is a hydrocarbon consisting of C and H.

(Confirmed by surface-enhanced Raman)
As the surface-enhanced Raman spectrometer, a transmission-type surface-enhanced sensor described in Patent No. 6179905 was used as a surface-enhanced Raman sensor, and NanoFinder 30 (Tokyo Instruments) was used as a confocal micro-Raman spectrometer. The measurement was performed with a transmission type surface-enhanced Raman sensor placed on the surface of the cut out base material. The measurement conditions were: Nd:YAG laser (532 nm, 1.2 mW), scan time (10 seconds), grating (800 Grooves/mm), and pinhole size (100 μm).

Samples 1 to 5, 8 to 16, 18, 19, 21, and 22 using octadecylphosphonic acid (C ₁₈ H ₃₉ O ₃ P) as a processing agent, and samples 1 to 5 using octadecylphosphonic acid (C ₁₂ H ₂₇ O Regarding sample 6 using _3P ), it was confirmed that one end of R was a methyl group by detecting a Raman shift of 2930 cm ^-1 .

Further, by detecting Raman shifts of 2850 and 2920 cm ^-1 , it was confirmed that R was a hydrocarbon consisting of C and H.

(Confirmation of M-O-P bond)
The M-O-P bond was confirmed using TOF-SIMS and surface-enhanced Raman spectroscopy.

(Confirmation of M-O-P by TOF-SIMS)
TOF-SIMS measurement conditions are: primary ion irradiation: ²⁰⁹ Bi ₃ ⁺⁺ , primary ion acceleration voltage 25 kV, pulse width 10.5 or 7.8 ns, with bunching, no charge neutralization, post-acceleration 9.5 kV, measurement range (Area): approximately 500×500 μm ² , Secondary ions to be detected: Positive, Negative, Cycle Time: 110 μs, Number of scans was 16. As the measurement results, a secondary ion mass spectrum derived from the combination of R-X and metal oxide element M (R-X-M) and a secondary ion mass spectrum (m/z) derived from M-O-P. This was confirmed by obtaining each. FIG. 9 shows a secondary ion mass spectrum in the negative electrode obtained by TOF-SIMS analysis of sample 3.

For samples 1 to 5, 11 to 14, and 16 and 22 containing Cr in the metal oxide layer and using octadecylphosphonic acid (C ₁₈ H ₃₉ O ₃ P) as a processing agent, in the negative mode, m/z =417 (C ₁₈ H ₃₈ PO ₅ Cr ^- ), m/z = 447, any ion of (C ₁₈ H ₃₇ P ₂ O ₅ Cr ^- ) (R-X-M), 146 (PO ₄ Cr ^- ) (O-M-O-P) ion was confirmed to be detected.

For samples 8, 9, and 15 containing Ti in the metal oxide layer and using octadecylphosphonic acid (C ₁₈ H ₃₉ O ₃ P) as a treatment agent, m/z = 413 (C ₁₈ H 39 ₃₈ PO ₅ Ti ⁻ ), m/z=443, any ion of (C ₁₈ H ₃₇ P ₂ O ₅ Ti ⁻ )(R−X−M), m/z=142(PO ₄ Ti ⁻ )( It was confirmed that ions of O-M-O-P) were detected.

For sample 10 containing Zr in the metal oxide layer and using octadecylphosphonic acid (C ₁₈ H ₃₉ O ₃ P) as a treatment agent, m/z = 456 (C ₁₈ H ₃₈ PO ₅ Zr ^- ), m/z = 486 (C ₁₈ H ₃₇ P ₂ O ₅ Zr ^- ) (R-X-M), m/z = 186 (PO ₄ Zr ^- ) (O-M-O- It was confirmed that ions of P) were detected.

Regarding sample 19, detection of the secondary ion mass spectrum derived from RXM and the secondary ion mass spectrum (m/z) derived from MOP was not confirmed.

For sample 6 using dodecylphosphonic acid (C ₁₂ H ₂₇ O ₃ P) as a treatment agent, in the negative mode, m/z = 332 (C ₁₂ H ₂₅ PO ₅ Cr ^- ) (R-X-M), It was confirmed that the ion 146(PO ₄ Cr ^- ) (O-M-O-P) was detected.

Regarding sample 7, in which octadecylphosphonic acid (C ₁₈ H ₃₉ O ₃ P) and phenylphosphonic acid (C ₆ H ₇ O ₃ P) were used as a treatment agent at a weight ratio of 1:1, regarding octadecylphosphonic acid It was confirmed that the same peak as Sample 1 was detected. For phenylphosphonic acid, m/z = 159 (C ₆ H ₈ O ₃ PCr ⁺ ) (R−X−M) in positive mode, m/z = 146 (PO ₄ Cr ⁻ ) (O− It was confirmed that ions of M-O-P) were detected.

(Confirmation of M-O-P by surface-enhanced Raman)
As the surface-enhanced Raman spectrometer, a transmission-type surface-enhanced sensor described in Patent No. 6179905 was used as a surface-enhanced Raman sensor, and NanoFinder 30 (Tokyo Instruments) was used as a confocal micro-Raman spectrometer. The measurement was performed with a transmission type surface-enhanced Raman sensor placed on the surface of the cut out base material. The measurement conditions were: Nd:YAG laser (532 nm, 1.2 mW), scan time (10 seconds), grating (800 Grooves/mm), and pinhole size (100 μm).

The signal originating from the M-O-P bond is derived from a Raman signal that estimates the bonding state of the M-O-P bond immobilized on the oxide layer in advance using Material Studio as a first-principles calculation software package. Attribution was made. Regarding structural optimization, the calculation conditions for first-principles calculations include software used (CASTEP), functional (LDA/CA-PZ), cutoff (830eV), K point (2*2*2), pseudopotential ( Norn-conserving), Density mixing (0.05), Spin (ON), and Metal (OFF). In addition, the Raman spectrum calculation was performed using the following software (CASTEP), functional (LDA/CA-PZ), cutoff (830eV), K point (1*1*1), pseudopotential (Norn-conserving), and density mixing ( All Bands/EDFT), Spin (OFF), and Metal (OFF).

For samples 1 to 7, 11 to 14, 16, and 22 containing chromium as the metal element of the base material, it was confirmed as follows that signals derived from each bonding state of M--O--P were detected.

By detecting two or more signals among Raman shifts 377 cm ^-1 , 684 cm ^-1 , 772 cm ^-1 , and 1014 cm ^-1 , a state in which one chromium atom is bound to phosphonic acid obtained by first-principles calculation ( It was confirmed that the M-O-P bond per phosphonic acid group contained one state: "bond 1").

By detecting two or more signals among the Raman shifts of 372 cm ^-1 , 433 cm ^-1 , 567 cm ^-1 , 766 cm ^-1 , and 982 cm ^-1 , it was determined that there were two chromium atoms in the phosphonic acid obtained by first-principles calculation. It was confirmed that the bonded state (two M--O--P bonds per phosphonic acid group: "bond 2") was included.

By detecting two or more signals among Raman shifts of 438 cm ^-1 , 552 cm ^-1 , 932 cm ^-1 , and 1149 cm ^-1 , a state in which three chromium atoms are bonded to phosphonic acid obtained by first-principles calculation ( It was confirmed that the M-O-P bond per phosphonic acid group contains three states: "bond 3").

FIG. 10 shows the transmission type surface-enhanced Raman spectrum of Sample 3. Sample 3 has Raman shifts of 377cm ^-1 , 684cm ^-1 , 772cm ^-1 , 1014cm ^-1 , 372cm ^-1 , 433cm ^-1 , 567cm ^-1 , 766cm ^-1 , 982cm ^-1 , 438cm ^-1 , 552cm ^-1 , 932c m Since signals of ⁻¹ and 1149 cm ⁻¹ were detected, it was confirmed that the chromium atom in the phosphonic acid contained all bonds 1, 2, and 3.

Regarding Sample 10 containing zirconium as the metal element of the base material, it was confirmed as follows that signals derived from each bonding state of M--O--P were detected.

By detecting two or more signals among Raman shifts 684 cm ^-1 , 770 cm ^-1 , 891 cm ^-1 , and 901 cm ^-1 , a state in which one zirconium atom is bonded to phosphonic acid obtained by first-principles calculation ( It was confirmed that the M-O-P bond per phosphonic acid group contained one state: "bond 1").

By detecting two or more signals among Raman shifts of 694 cm ^-1 , 716 cm ^-1 , 1272 cm ^-1 , 1305 cm ^-1 , and 1420 cm ^-1 , it was determined that two zirconium atoms were present in the phosphonic acid obtained by first-principles calculation. It was confirmed that the bonded state (two M--O--P bonds per phosphonic acid group: "bond 2") was included.

By detecting two or more signals among Raman shifts of 559 cm ^-1 , 943 cm ^-1 , 1006 cm ^-1 , and 1110 cm ^-1 , a state in which three zirconium atoms are bonded to phosphonic acid obtained by first-principles calculations ( It was confirmed that the M-O-P bond per phosphonic acid group contains three states: "bond 3").

Since a Raman shift signal was detected in sample 10, it was confirmed that the zirconium atom in the phosphonic acid contained all bonds 1, 2, and 3.

Claims (14)

a base material whose surface contains a metal element;
a metal oxide layer formed on the base material;
A sanitary equipment member comprising an organic layer provided on the metal oxide layer,
The metal element is at least one selected from the group consisting of Cr, Zr, and Ti,
The metal oxide layer contains at least one metal element selected from the group consisting of Cr, Zr, and Ti and an oxygen element,
The organic layer is present on the surface of the sanitary equipment member,
The sanitary equipment member has a surface that is
When measured by X-ray photoelectric spectroscopy (XPS) using wide scan analysis according to condition 1, the metal element (M), phosphorus atom (P), oxygen atom (O), and carbon atom (C ) is detected, and
When measured according to condition A by time-of-flight secondary ion mass spectrometry (TOF-SIMS), the general formula RX (R is a hydrocarbon group or an atom other than carbon at one or two positions within the hydrocarbon group) is a group that does not contain at least one atom or functional group selected from the group consisting of a halogen atom, a sulfonic acid group, a hydroxyl group, a carboxylic acid group, an amino group, and an ammonium group, and X is a phosphonic acid group , phosphoric acid group, and phosphinic acid group) is detected,
The sanitary equipment component is used in a bathroom, toilet space, restroom, washroom, or kitchen, and is characterized in that limescale is removed in a test conducted using the following test method. , sanitary equipment components.
(Condition 1)
X-ray conditions: Monochromatic AlKα rays (output 25W)
Photoelectron extraction angle: 45°
Analysis area: 100μmφ
Operation range: 15.5-1100eV
(Condition A)
Primary ions to be irradiated: ²⁰⁹ Bi ³⁺⁺
Primary ion acceleration voltage: 25kV
Pulse width: 10.5or7.8ns
Bunching: Yes Charge neutralization: None Post-stage acceleration: 9.5kV
Measurement range (area): Approximately 500 x 500 μm ²
Secondary ions to detect: Positive and Negative
Cycle time: 110μs
Number of scans: 16
(Test method)
Perform the following steps 1) to 4) in that order.
1) After immersing the sanitary equipment member in 70° C. hot water for 2 hours, the surface is rinsed with running water, and then the water on the surface is removed.
2) Drop 20 μl of tap water onto the surface of the sanitary equipment member and leave it indoors for 24 hours to form limescale on the surface of the sanitary equipment member.
3) Slide a dry cloth back and forth 10 times on the surface where limescale has been formed while applying a load of 100 gf/cm ² .
4) Visually judge whether water scale has been removed from the surface after sliding. The sanitary equipment member according to claim 1, wherein in the organic layer, one end of R (the end on the side that is not bonded to X) is made of C and H. The sanitary equipment member according to claim 2, wherein the R is a hydrocarbon group consisting of C and H. The sanitary equipment member according to any one of claims 1 to 3, wherein in the organic layer, X is phosphonic acid. The sanitary equipment member according to any one of claims 1 to 4, wherein the organic layer is a monomolecular layer. A sanitary equipment component according to claim 5, wherein the organic layer is a self-assembled monolayer. The hygiene according to any one of claims 1 to 6, wherein the phosphorus atom concentration calculated from the peak area of the P2p spectrum measured according to the condition 1 by the XPS is 1.0 at% or more and 10 at% or less. Equipment parts. The sanitary equipment member according to claim 7, wherein the phosphorus atom concentration is 1.5 at% or more. Oxygen atom/metal atom concentration ratio (O/M ratio) on the surface of the sanitary equipment member, calculated from the peak areas of the O1s spectrum and metal spectrum measured according to Condition 1 by X-ray photoelectron spectroscopy (XPS). A sanitary equipment component according to claim 7 or 8, wherein: is greater than 1.7. The sanitary equipment member according to claim 9, wherein the O/M ratio is 1.8 or more. Any one of claims 1 to 10, wherein the carbon atom concentration on the surface of the sanitary equipment member is 43 at% or more, calculated based on the peak area of the C1s spectrum measured according to the condition 1 by the XPS. Sanitary equipment components described in. The sanitary equipment member according to any one of claims 1 to 11, wherein the sanitary equipment member is a water faucet. The sanitary equipment member according to claim 12, wherein the sanitary equipment member is a faucet that spouts hot water . A method for manufacturing a sanitary equipment member according to claims 1 to 13,
a step of preparing a base material;
A process of increasing the degree of oxidation on the surface of the base material,
A step of applying a compound represented by the general formula RX (R is a hydrocarbon group, and X is at least one selected from a phosphonic acid group, a phosphoric acid group, and a phosphinic acid group);
including methods.