JP2023104911A - sanitary ware - Google Patents

Abstract

To provide sanitary ware having both excellent antifouling properties and high durability.SOLUTION: The sanitary ware comprises a sanitary ware substrate and a glaze layer provided on a surface of the substrate, and is characterized in that: a surface of the glaze layer has an arithmetic mean roughness Ra of 0.03 μm or more and 2.5 μm or less; a surface of the sanitary ware contains perfluoropolyether chains; a ratio of the number of all fluorine atoms having C-F bonds to a total number of carbon atoms having the C-F bonds and oxygen atoms bonded thereto in the perfluoropolyether chains is 1.1 or more and 1.7 or less, which ratio is obtained through peak separation of a spectrum obtained by performing an X-ray photoelectron spectroscopy (XPS) measurement of the surface of sanitary ware; and a ratio of the number of carbon atoms having CF3 bonds in the perfluoropolyether chains to the total number of carbon atoms having C-F bonds in the perfluoropolyether chains is 20 at% or less, which ratio is obtained through the peak separation.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to sanitary ware having both good antifouling properties and high durability for use in an environment where water may be splashed.

A member used around water (so-called water-related member) is used in an environment where water exists. Therefore, water tends to adhere to the surface of the plumbing member. 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. In addition, stains such as protein, sebum, microorganisms such as mold, and metallic soap tend to adhere to the surface of the plumbing member. In order to prevent dirt such as limescale from adhering to the surface of a plumbing member and to improve the removability of the dirt, there is known a technique of modifying the surface of the member by coating it with a protective layer or the like.

However, when a protective layer is provided on a plumbing member, there is a problem that the surface of the member is colored, or the appearance of the member is damaged due to damage or peeling of the protective layer. In order to solve this problem, conventionally, a monomolecular film that chemically bonds with plumbing parts has been used. Since the monomolecular film is a thin layer that cannot be visually recognized, the function of the monomolecular film can be imparted without impairing the appearance of the member by providing the monomolecular film. In addition, since the monomolecular film chemically bonds with the plumbing parts, the durability of the film is also improved. For example, it is known that a monomolecular film containing a fluoroalkylsilane compound protects the surface of a member and also has an antifouling effect. For example, Japanese Patent Application Laid-Open No. 2005-206455 (Patent Document 1) describes that a wear-resistant antifouling ceramic product can be obtained by forming a film containing a fluoroalkylsilane compound on the surface of a tile. It is

On the other hand, it is difficult to prevent dirt from adhering to the surface of the plumbing member, and the dirt is removed by cleaning. For example, in sanitary ware, attempts have been made to increase the smoothness of the surface so that stains can be easily removed. However, the adherence of contaminants may roughen the surface and reduce the hydrophilicity of the surface. There is still a demand for sanitary ware from which such adhered dirt can be easily removed. In the case of removing adhered dirt and limescale, strong alkaline or strong acidic detergents are used, the force required for wiping is increased, and the number of times of wiping is increased. In other words, the plumbing member is placed in a high-load usage environment. Therefore, a thin film such as a monomolecular film containing the above-described fluoroalkylsilane compound may lose its function early. Therefore, in recent years, a technique has been proposed in which a compound containing a perfluoropolyether chain, which is superior in adhesion and durability to a plumbing member compared to a fluoroalkylsilane compound, is applied to the member surface.

For example, Japanese Patent Application Laid-Open No. 2011-021088 (Patent Document 2) describes an antifouling paint containing a main agent made of perfluoropolyether and a solvent containing an alkane having a specific average molecular weight on the surface of sanitary ware having a glaze layer. is applied to form an antifouling layer. According to Patent Document 2, perfluoropolyether contains CF ₃ side chains (paragraphs 0013-0014), and smoothness can be improved by applying an antifouling paint containing this perfluoropolyether and an alkane with a specific average molecular weight. (Paragraph 0016).

In addition, in Japanese Patent Laid-Open No. 2021-113323 (Patent Document 3), a surface treatment agent containing a perfluoropolyether group-containing compound is applied to the surface of chemically strengthened glass, thereby curing with good friction durability. It is described that layers are formed. Specifically, —(OC ₆ F ₁₂ ) _a —(OC ₅ F ₁₀ ) _b —(OC ₄ F ₈ ) _c —(OC ₃ F ₆ ) _d —(OC ₂ F) contained in the perfluoropolyether group ₄ ) In _e- (OCF ₂ ) _f- , it is essential that the e/f ratio is 0.9 or more, which enhances the water and oil repellency of the cured layer. On the other hand, if the e/f ratio is too low, the lubricity (surface slipperiness) of the hardened layer is reduced, and if the e/f ratio is too high, the coefficient of dynamic friction of the hardened layer increases, resulting in sufficient friction durability. It is described that the characteristics cannot be obtained (Paragraph 0039). More specifically, the e/f ratio is preferably 1.0 or more (paragraph 0039). It is described that the cured layers formed by applying the surface treatment agents of Examples 1, 2 and 3 containing perfluoropolyether group-containing compounds showed good results in the eraser friction resistance test.

JP 2005-206455 A Japanese Unexamined Patent Application Publication No. 2011-021088 JP 2021-113323 A

The present inventors have found that sanitary ware containing perfluoropolyether chains on the surface, which is generally considered to have high water repellency and durability, loses its function when used in a high-load environment. Confirmed there is something. In addition, the present inventors have found a new composition of sanitary ware that has both good antifouling properties and higher durability, especially sliding resistance. In other words, by providing specific perfluoropolyether chains on the uneven surface unique to sanitary ware, it is possible to effectively prevent the adhesion of dirt, and in general, it is possible to prevent dirt that requires cleaning under a high-load environment. It has been found that even if there is, it can be removed easily, that is, with a small cleaning load. Further, the present inventors have found that sanitary ware can be obtained which has high durability, especially sliding resistance, against the load of cleaning when dirt is removed, and which has excellent water repellency. The present invention is based on these findings.

The sanitary ware according to the present invention is
It comprises a substrate for sanitary ware and a glaze layer provided on the surface of the substrate,
The glaze layer has a surface arithmetic mean line roughness Ra of 0.03 μm or more and 2.5 μm or less,
The surface of the sanitary ware comprises perfluoropolyether chains,
All carbon atoms having C—F bonds and bonded thereto in the perfluoropolyether chain, obtained by peak separation of the spectrum obtained by X-ray photoelectron spectroscopy (XPS) measurement of the surface of the sanitary ware The ratio of the number of all fluorine atoms having a C-F bond to the total number of oxygen atoms is 1.1 or more and 1.7 or less,
The ratio of the number of carbon atoms having a _CF3 bond in the perfluoropolyether chain to the total number of carbon atoms having a CF bond in the perfluoropolyether chain obtained by the peak separation is 20 at% or less. characterized by being

According to the present invention, by providing specific perfluoropolyether chains on the surface of the glaze layer having a specific surface roughness, it is possible to use a strong alkaline or strong acid detergent in a high-load environment (when removing stains). It has excellent durability against sliding force and excellent water repellency, even when used in environments such as using, wiping with strong force, and wiping many times. To provide sanitary ware capable of maintaining stainability. In addition, according to the present invention, the above-described good antifouling property and high durability are achieved while maintaining a beautiful appearance that takes advantage of the inherent properties of sanitary ware (e.g., texture, glossiness, hardness, etc.). Sanitary ware is provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is the schematic diagram which shows an example of the sanitary ware by this invention, and its enlarged view. 1 is a schematic diagram of a sanitary ware surface before and after applying a load to the surface; FIG. FIG. 3 is a diagram showing the XPS spectrum and peak separation results of the surface of sanitary ware produced using treatment liquid a. FIG. 3 is a diagram showing the results of XPS spectrum and peak separation of the sanitary ware surface produced using the treatment liquid b. FIG. 4 is a diagram showing the results of XPS spectrum and peak separation of the surface of sanitary ware produced using treatment liquid c. FIG. 4 is a diagram showing the results of XPS spectrum and peak separation of the surface of sanitary ware produced using treatment liquid d. FIG. 4 is a diagram showing the results of XPS spectrum and peak separation of the sanitary ware surface produced using the treatment liquid e. FIG. 4 is a diagram showing the results of XPS spectrum and peak separation of the sanitary ware surface produced using the treatment liquid f. FIG. 4 is a diagram showing the results of XPS spectrum and peak separation of the sanitary ware surface produced using the treatment liquid g.

Sanitary Ware In the present invention, the term "sanitary ware" means ceramic products used in bathrooms, toilet spaces, restrooms, washrooms, kitchens, or the like. Specifically, it means a toilet bowl, a urinal, a toilet bowl bowl, a toilet bowl tank, a washbasin, a hand basin, and the like.

FIG. 1A is a schematic diagram showing the cross-sectional structure of sanitary ware according to the present invention, and FIG. 1B is an enlarged view of the circled portion in FIG. 1A. A sanitary ware 10 according to the present invention comprises a base 1 for sanitary ware and a glaze layer 2, as shown in FIG. 1A. The sanitary ware 10 contains perfluoropolyether chains 3 on the surface of the glaze layer 2 .

Base material for sanitary ware In the present invention, the base material 1 for sanitary ware is not particularly limited, and a known base material for sanitary ware used for the sanitary ware 10 can be used. The base material 1 for sanitary ware may be a conventionally known base material for sanitary ware obtained by preparing silica sand, feldspar, limestone, clay, or the like as raw materials, molding, and firing.

In one embodiment of the present invention, an intermediate layer made of another material having properties different from those of the sanitary ware material 1 may be provided between the glaze layer 2 and the sanitary ware material 1 . As a result, air bubbles entering the glaze layer 2 from the ceramic body can be suppressed during the firing process during manufacture, and the glaze layer 2 can be formed not only with excellent appearance but also with excellent cleanability.

Glaze Layer In the present invention, the surface arithmetic mean line roughness Ra of the glaze layer 2 is from 0.03 μm to 2.5 μm. Preferably, the surface arithmetic mean line roughness Ra of the glaze layer 2 is 0.03 μm or more and 1.5 μm or less. More preferably, the surface arithmetic mean line roughness Ra of the glaze layer 2 is 0.03 μm or more and 1.0 μm or less. The arithmetic mean line roughness Ra is measured according to JIS-B0633 (2001) "7. Method and procedure for evaluation by a stylus type surface roughness measuring instrument", Obtained using a needle-type surface roughness measuring device. In the present invention, the surface arithmetic mean line roughness Ra of the glaze layer 2 is considered to be the same as the surface arithmetic mean line roughness Ra of the sanitary ware 10 . Therefore, by measuring the arithmetic mean line roughness Ra of the surface of the sanitary ware 10, the arithmetic mean line roughness Ra of the glaze layer 2 can be obtained. The reason for this is that the perfluoropolyether chains 3 contained in the surface of the sanitary ware 10 have a height that does not affect the surface roughness of the glaze layer 2 . Specifically, the perfluoropolyether chain 3 preferably has a height of 20 nm or less. In the present invention, the glaze layer 2 may have a composition generally understood by those skilled in the art as a glaze layer, as long as the surface satisfies the above Ra. According to one aspect of the present invention, the glaze layer 2 has a composition, in terms of oxide, given in Table 1 below.

According to a further aspect of _the present invention, the glaze layer _{2 contains Fe2O3, TiO2, BaO, B2O3, Li2O, Sb2O3 , in addition to the ingredients} listed in Table 1 above. , CuO, MnO, NiO, CoO, MoO ₃ , SnO ₂ , PbO and the like. Also, the glaze layer 2 may contain particles. The particles include crystalline particles contained in the glaze raw material and crystalline particles precipitated by firing. Particle materials include zircon, quartz, diopside, and anorthite.

In the present invention, the color of the glaze layer 2 is not particularly limited as long as the composition of the glaze layer 2 is within the range shown in Table 1. Examples of colors of the glaze layer 2 include white, black, ivory, pink, gray, brown, beige, green, red, and blue.

In the present invention, the arithmetic mean line roughness Ra (0.03 μm or more and 2.5 μm or less) of the surface of the glaze layer 2 may be obtained by processing the surface of the glaze layer 2 so that Ra satisfies the above range. Alternatively, the surface of the base material 1 for sanitary ware may be processed so that the Ra of the glaze layer 2 thereon satisfies the above range.

In the present invention, a primer layer may be provided on the surface of the glaze layer 2 . By providing the primer layer, it is possible to form perfluoropolyether chains at a high density on the surface of the glaze layer. The primer layer preferably does not affect Ra on the surface of the glaze layer 2, and its thickness is preferably nano-order. Specifically, it is 20 nm or less, and more preferably 10 nm or less. The primer layer is preferably a layer containing metal oxides such as SiO ₂ , TiO ₂ and Al ₂ O ₃ generated by hydroxyl groups present on the surface.

Manufacture of sanitary ware In the present invention, sanitary ware 10 is produced, for example, by first forming a glaze layer 2 on a sanitary ware substrate 1, and then treating the surface of the glaze layer 2 with perfluoropolyether chains 3. It can be manufactured by applying a liquid. Specifically, it can be produced by the following method.

First, a molded body to be the base material 1 for sanitary ware is prepared. This is obtained by casting a known slurry for sanitary ware, which is prepared using silica sand, feldspar, limestone, clay, etc. as raw materials, in a mold such as gypsum. After the compact is dried, it is glazed as described below.

The raw material of the glaze forming the glaze layer 2 is not particularly limited as long as the arithmetic mean line roughness Ra of the surface of the glaze layer 2 can be 0.03 μm or more and 2.5 μm or less. The composition of the glaze layer may be realized. As the glaze raw material, mixtures of natural mineral particles such as silica sand, feldspar and limestone, pigments such as cobalt compounds and iron compounds, and emulsifiers such as zirconium silicate and tin oxide may be used. In one aspect of the present invention, the composition of the glaze raw material is, for example, 10 wt% to 30 wt% feldspar, 15 wt% to 40 wt% silica sand, 10 wt% to 25 wt% calcium carbonate, corundum, talc, dolomite, and zinc white. , 10 wt% or less each, and a total of 15 wt% or less of emulsifiers and pigments. The glaze can be obtained, for example, by melting the glaze raw material as described above at a high temperature and then rapidly cooling it to vitrify it.

The glaze described above is applied to the dried compact, and then dried and fired to form the glaze layer 2 on the substrate 1 for sanitary ware. The firing temperature can be, for example, a temperature of 1000° C. or higher and 1300° C. or lower at which the glaze softens.

The surface of the formed glaze layer 2 may be subjected to surface treatment, if necessary, within a range in which Ra satisfies the above range. For example, blasting or etching may be performed. In the blasting, the surface of the glaze layer 2 satisfying the aforementioned range of Ra can be obtained by controlling the material/shape/grain size of the media used, the processing time per unit area, whether it is dry or wet, and the like. In the etching process, the surface of the glaze layer 2 having Ra satisfying the above range can be obtained by controlling the pattern of the photomask and the concentration/type/temperature/presence/absence of stirring of the etchant. This makes it possible to improve the glossiness of the surface, or reduce the glossiness to make it matte.

The surface of the formed glaze layer 2 may have fine roughness in minute regions within the range of Ra satisfying the above range. For example, the arithmetic mean surface roughness Sa at a viewing angle of 5.0 μm×5.0 μm when observed using a scanning probe microscope (SPM) is preferably 0.03 μm or less. The arithmetic mean surface roughness Sa of the surface of the glaze layer 2 is obtained using a coordinate measuring machine described in JIS-B0681-6 (2014) according to JIS-B0681-2 (2018). When the flexibility of the perfluoropolyether chains 3 provided on the surface of the glaze layer 2 having such fine roughness Sa is high, the chains 3 can only follow the surface shape in the range where Ra satisfies the above range. In addition, it can follow the surface shape having fine roughness in a minute area, and is considered to be excellent in sliding resistance and resistance to alkali components contained in detergents and the like (hereinafter referred to as alkali resistance). It is also conceivable that the presence of fine roughness in the fine regions can further improve the water repellency and obtain more excellent antifouling properties.

In the present invention, in addition to the above-described sanitary ware substrate and glaze layer manufacturing method, for example, JP 2021-134133, JP 2020-147492, WO99/61392, etc. It is possible to use the method for manufacturing the substrate and glaze layer for sanitary ware. In the present specification, by referring to the above-mentioned publications, the method for producing the sanitary ware substrate and the glaze layer described in these publications can be used in the present invention. As such, it is incorporated into the description of this specification.

Next, a treatment liquid containing a compound containing a perfluoropolyether chain 3, which will be described later, is applied to the surface of the glaze layer 2 formed on the base material 1 for sanitary ware. As a method for applying the treatment liquid containing the compound containing the perfluoropolyether chain 3, a known method can be used. For example, a treatment liquid containing a compound containing a perfluoropolyether chain 3 can be applied by dipping, spin coating, wiping, vacuum deposition, spray gun, or the like. After applying a treatment liquid containing a compound containing a perfluoropolyether chain 3 to the surface of the glaze layer 2, it is dried and, if necessary, cured. and a sponge, followed by thorough rinsing with ultrapure water to obtain sanitary ware 10 containing perfluoropolyether chains 3 on the surface of glaze layer 2 .

In the present invention, before applying a treatment liquid containing a compound containing perfluoropolyether chains 3 to the surface of the glaze layer 2, pretreatment is performed to remove stains present on the surface and to activate hydroxyl groups on the surface. good too. As a pretreatment for activating hydroxyl groups on the surface, ultrasonic cleaning using an alkaline solution, particle polishing using fine metal particles, or the like can be used.

In the present invention, a primer layer may be formed on the surface of the glaze layer 2, and after pretreatment if necessary, a treatment liquid containing a compound containing perfluoropolyether chains 3 may be applied. The primer layer can be formed by, for example, a sol-gel method, physical vapor deposition (PVD), chemical vapor deposition (CVD), or the like.

ここで、ｐ，ｑ，ｒ，ｓは繰り返し単位の数、すなわち０以上の整数であり、ｐ，ｑ，ｒ，ｓの和は３～２００であり、式中の各繰り返し単位がランダムに結合した鎖でもよく、各繰り返し単位からなるそれぞれの高分子鎖同士が結合した鎖でもよい。Ｒ_ｆ１はフッ素原子、またはフッ素原子が単結合した炭素原子を含む炭素原子数が１以上の有機基を表し、Ｒ_ｆ２はフッ素原子が単結合した炭素原子を含む炭素原子数が１以上の有機基を表す。。 As the treatment liquid containing the compound containing the perfluoropolyether chain 3, any liquid can be used as long as the sanitary ware of the present invention can be produced. As a compound containing a perfluoropolyether chain 3, one or more of each ether bond, which is a repeating unit such as CF ₂ O, C ₂ F ₄ O, C ₃ F ₆ O, C ₄ F ₈ O, is randomly bonded Compounds containing chains are included. A specific example of the compound containing the perfluoropolyether chain 3 is a compound containing the structure shown in Formula 1 below.

Here, p, q, r, s are the number of repeating units, that is, an integer of 0 or more, the sum of p, q, r, s is 3 to 200, and each repeating unit in the formula is randomly bonded It may be a chain in which each polymer chain composed of each repeating unit is bonded to each other. R _f1 represents a fluorine atom or an organic group having 1 or more carbon atoms containing a carbon atom to which a fluorine atom is single-bonded; R _f2 represents an organic group having 1 or more carbon atoms containing a carbon atom to which a fluorine atom is single-bonded represents a group. .

（式中、ｌ：ｍ：ｎ＝２３．２：２２．３：０．４（平均値）であり、式中の繰り返し単位はランダムに配列している。）

（式中、ｌの平均値は２２．９である。）、

（式中、ｌの平均値は２３．２である。）、

（式中、ｌの平均値は１８である。）

（式中、ｌの平均値は２３．４である。）。 More specific compounds containing the perfluoropolyether chain 3 include compounds containing structures represented by formulas 2 to 6 below.

(In the formula, l:m:n=23.2:22.3:0.4 (average value), and the repeating units in the formula are randomly arranged.)

(wherein the average value of l is 22.9),

(wherein the average value of l is 23.2),

(Where the average value of l is 18.)

(wherein the average value of l is 23.4).

The compound containing perfluoropolyether chain 3 is preferably a compound containing perfluoropolyether chain 3 and at least one Si atom. A compound in which a perfluoropolyether chain 3 and at least one reactive silyl group are bonded is more preferable. This facilitates bonding between the surface of the glaze layer 2 and the perfluoropolyether chains 3 . The Si atom of the reactive silyl group may be bonded to one end of the perfluoropolyether chain 3 or to both ends, but is preferably bonded to one end. A reactive silyl group is a functional group in which an organic group containing no fluorine atom on a Si atom is bonded to a hydroxyl group or a hydrolyzable group. The hydrolyzable groups are specifically alkoxy groups, halogeno groups and the like, and more specifically -OCH ₃ , -OCH ₂ CH ₃ , -OCOCH ₃ , -Cl and the like.

Any solvent can be used for the treatment liquid as long as it can be mixed with the perfluoropolyether chain 3. Examples thereof include fluorine-based solvents, hexane, chain ether compounds, and cyclic ether compounds.

Perfluoropolyether Chains The surface of the sanitary ware 10 according to the invention comprises perfluoropolyether chains 3 . The perfluoropolyether chain 3 is a chain containing, in a repeating structure, carbon atoms to which fluorine atoms are bonded and ether bonds _in which the carbon atoms are bonded via oxygen _atoms . O]- (x is a natural number). Specifically, each ether bond, which is a repeating unit such as (CF ₂ )—O, (C ₂ F ₄ )—O, (C ₃ F ₆ )—O, (C ₄ F ₈ )—O, is one The above are randomly connected chains. In the present invention, the total number of repeating units is preferably as large as possible, but is more preferably 200 or less.

The presence of the perfluoropolyether chain 3 on the surface of the sanitary ware 10 can be identified, for example, by the following analysis method.

The presence of perfluoropolyether chains 3 on the surface of sanitary ware 10 can be identified by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectroscopy (TOF-SIMS).

First, the surface of sanitary ware is evaluated by X-ray photoelectron spectroscopy (XPS) to obtain C1s and F1s spectra. In this spectrum, a peak of a fluorine atom having a C—F bond in F1s (peak position: 687 eV to 690 eV) is obtained, and a peak of a carbon atom having a C—F bond in C1s (peak position: 289 eV to 297 eV) is obtained. The results show that the surface of the sanitary ware contains C—F bonds. Examples of compounds containing CF bonds include perfluoropolyether chain-containing compounds and fluoroalkylsilane compounds. In addition, the XPS measurement is performed by “acquisition of XPS spectrum” using “XPS measurement conditions” described later.

The sanitary ware surface is then evaluated by TOF-SIMS. As a TOF-SIMS device, TOF. SIMS5 (ION-TOF) can be used. TOF-SIMS is an analysis technique for detecting secondary ions generated from a sample surface when the sample surface is irradiated with pulsed primary ions emitted from a primary ion source. The types of secondary ions generated and detection sensitivity vary depending on the composition and chemical structure of the sample surface. By visualizing the distribution of various secondary ions on the sample surface, it is possible to estimate the composition and chemical structure distribution on the sample surface.

By evaluating the surface of sanitary ware by TOF-SIMS using the following measurement conditions, horizontal axis: mass number (m / z, that is, mass m divided by charge z), vertical axis: secondary ion A secondary ion mass spectrum in terms of intensity (number of counts) can be obtained.
[TOF-SIMS measurement conditions]
Primary ion source: Bi ³⁺
Primary ion acceleration voltage: 30 keV
Primary ion current value: 0.2 pA (at 10 kHz)
Primary ion punching: Available Measurement range: 500 μm×500 μm
Cycle time: 400 μs
Number of pixels: 128 x 128 pixels
Degree of vacuum: ^9-8 hPa
Secondary ion: Negative ion
Neutralization Gun: Yes

From the C1s and F1s peaks obtained by XPS, it can be seen whether or not the surface of the sanitary ware 10 contains C—F bonds. When the surface of the sanitary ware 10 is found to contain C—F bonds by XPS, the surface of the sanitary ware 10 is analyzed from the secondary ion mass spectrum obtained by TOF-SIMS under the above measurement conditions. It is possible to confirm that it contains fluoropolyether chains 3 . Specifically, on the high mass side where m / z of the secondary ion mass spectrum obtained by TOF-SIMS is several hundred or more, if there are fragments that periodically appear at equal mass intervals, repeating units from that mass interval can deduce the molecular formula of Similar assumptions can be made for the case where a plurality of repeating units are present. Based on the existence of a C—F bond obtained by XPS and the degree of agreement between accurate mass and isotope obtained by TOF-SIMS, the molecular formula of the repeating unit is C _x F _y O _z (where x, y, and z are integers of 1 or more). , where y=2x), it is known that the repeating unit contains a perfluoroether. Moreover, at least the total number of repeating units can be determined from the fragments that appear periodically at equal mass intervals. From the above TOF-SIMS analysis, it is found that the surface of the sanitary ware 10 contains perfluoropolyether chains 3 when the repeating units contain perfluoroether and the total number of repeating units is at least 3 or more.

The perfluoropolyether chains 3 are preferably bonded to the glaze layer via Si atoms. More preferably, the perfluoropolyether chain 3 is bonded to the glaze layer via a plurality of Si atoms. This improves the adhesion between the perfluoropolyether chain 3 and the glaze layer 2 . Si atoms are preferably bonded to the ends of perfluoropolyether chains 3 . More preferably, Si atoms are bonded to the ends of the perfluoropolyether chain 3 . Although Si atoms may be bonded to both ends of the perfluoropolyether chain 3, it is more preferable to bond Si atoms to one end of the perfluoropolyether chain 3. The Si atoms bonded to the perfluoropolyether chains 3 were generated by activating the surface of the glaze layer even though they were derived from the reactive silyl groups bonded to the perfluoropolyether chains 3 contained in the raw material. Si atoms may be used.

The hydroxyl group or hydrolyzable group contained in the reactive silyl group preferably functions as a bonding point with the glaze layer 2 . That is, the hydroxyl group contained in the reactive silyl group, the hydroxyl group obtained by hydrolyzing the hydrolyzable group, or the hydrogen atom contained in the hydroxyl group is the functional group (hydrogen atom or hydroxyl group, etc.). This allows the perfluoropolyether chains 3 to bond with the surface of the glaze layer 2 . Perfluoropolyether chains 3 are preferably bonded to glaze layer 2 via Si atoms. In the present invention, the reactive silyl groups preferably contain many hydroxyl groups or hydrolyzable groups. This improves the adhesion between the perfluoropolyether chain 3 and the glaze layer 2 .

The fact that the perfluoropolyether chain 3 is bonded to the glaze layer 2 via Si atoms can be confirmed by methods such as surface-enhanced Raman spectroscopy (SERS), ¹⁹ Si-NMR and infrared spectroscopy (IR). can be specified.

The ratio of the number of fluorine atoms to the total number of carbon atoms and oxygen atoms in the perfluoropolyether chain. Ratio of the number of all fluorine atoms having a CF bond to the total number of all carbon atoms having a CF bond and oxygen atoms bonded thereto in the resulting perfluoropolyether chain 3 (hereinafter, " F/(C+O) ratio") is 1.1 or more and 1.7 or less. The F/(C+O) ratio is preferably 1.1 or more and 1.5 or less. Thereby, the perfluoropolyether chain 3 has excellent flexibility and excellent water repellency. The reason for this is considered as follows, but the present invention is not limited to this. The perfluoropolyether chain is believed to contain fluorine, oxygen and carbon atoms, with fluorine and oxygen atoms attached to the carbon atoms. In general, atoms bonded to carbon atoms are positioned at the vertices of a regular tetrahedral structure, so they can rotate freely around the carbon single bond. Therefore, it can take an infinite number of conformations. If the perfluoropolyether chain contains an ether bond, the presence of an oxygen atom between the two carbon atoms bonded to the oxygen atom of the ether bond makes it difficult for the interaction to work, and the energy due to the position of the twist there is almost no difference. Therefore, an organic chain containing an ether bond can relatively freely rotate around a carbon-oxygen single bond. For example, a perfluoropolyether chain having many ether bonds can change its shape with a higher degree of freedom than a fluoroalkyl chain having no ether bond. That is, it is considered to be excellent in flexibility. Moreover, the surface energy of the sanitary ware surface decreases as the ratio of the number of fluorine atoms contained in the perfluoropolyether chain increases. That is, it is considered to be excellent in water repellency. The F/(C+O) ratio indicates the abundance ratio of fluorine atoms and oxygen atoms when the number of carbon atoms is constant. Therefore, the larger the value of the F/(C+O) ratio, the higher the proportion of fluorine atoms, that is, the better the water repellency. Conversely, the smaller the value of the F/(C+O) ratio, the higher the proportion of oxygen atoms. That is, it means excellent flexibility. For example, when the proportion of oxygen atoms present in the perfluoropolyether chain 3 is large, the proportion of fluorine atoms is correspondingly small, so that the flexibility increases but the water repellency decreases. In this way, the water repellency and flexibility of the perfluoropolyether chain are in a trade-off relationship. It can be said that balance is important. Therefore, the excellent water repellency and flexibility possessed by the perfluoropolyether chain 3 allow the sanitary ware according to the present invention to have high antifouling properties and long-term durability, especially sliding resistance. A method for calculating the F/(C+O) ratio will be described later.

The ratio of the number of carbon atoms with CF3 bonds to the total number of carbon atoms with CF bonds _in the perfluoropolyether chain In the present invention, the surface of sanitary ware is measured by X-ray photoelectron spectroscopy (XPS) The ratio of the number of carbon atoms having a _CF3 bond to the number of all carbon atoms having a CF bond in the perfluoropolyether chain 3 (hereinafter referred to as “ _CF3 (also referred to as "the ratio of the number of carbon atoms having a bond") is 20 atomic % or less. It is believed that the excellent flexibility of the perfluoropolyether chain 31 is maintained when the ratio of the number of carbon atoms having CF ₃ bonds is 20 at % or less. In other words, it is considered that the flexibility of the perfluoropolyether chain 31 decreases when the ratio of the number of carbon atoms having CF ₃ bonds exceeds 20 at %. The reason is that when the ratio of the number of carbon atoms having CF ₃ bonds exceeds 20 at %, the possibility of including perfluoroalkyl chains in the side chains increases. As a result, steric hindrance is likely to occur, and the degree of freedom of rotation of the ether bond contained in the perfluoropolyether chain, which is the main chain, is reduced, and it is thought that the flexibility is reduced.

The sanitary ware according to the present invention is considered to have the following effects by including the above-mentioned specific perfluoropolyether chains 3 on the surface of the glaze layer having a unique uneven shape.

In the sanitary ware of the present invention, the above-mentioned specific perfluoropolyether chains 3 have an excellent balance between water repellency and flexibility, so that the perfluoropolyether chains follow the unique irregularities on the surface of the glaze layer 2. and can exhibit antifouling properties. The sanitary ware of the present invention has a perfluoropolyether chain with excellent water repellency, so that it can repel dirt and water present in the usage environment of the sanitary ware. Therefore, it is possible to prevent the adherence of dirt and limescale to the surface of the sanitary ware. That is, the sanitary ware of the present invention has excellent antifouling properties. In addition, the sanitary ware of the present invention can maintain its function for a long period of time even under high-load environments by being provided with perfluoropolyether chains having excellent flexibility. That is, the sanitary ware of the present invention has excellent durability. As described above, the sanitary ware of the present invention has excellent water repellency and flexibility due to the above-mentioned specific perfluoropolyether chain 3, so even when used in a high-load environment, can exhibit antifouling properties over a long period of time. FIG. 2A is a cross-sectional view of an example of the sanitary ware of the present invention when a load is applied to the surface with a sponge or the like and after that. It is considered that the load applied to the surface of the sanitary ware by a sponge or the like is applied downward and laterally (right and left) when removing dirt adhering to the surface of the sanitary ware. The sanitary ware 10 of the present invention has a unique effect of being able to disperse or release the load applied to the joints between the perfluoropolyether chains 3 and the glaze layer 2 due to the highly flexible surface structure. demonstrate. Therefore, it is possible to suppress (reduce) wear of the perfluoropolyether chain 3 and maintain the anti-sliding function for a long period of time. In particular, the perfluoropolyether chain 3 can maximize its excellent flexibility when the force applied in the lateral direction is concentrated on the uneven convex portions. In addition, in the aspect in which the perfluoropolyether chains 3 form a film, the flexibility is further enhanced, the wear of the film is further suppressed, and the sliding resistance function is maintained for a longer period of time. maintained.

As described above, the sanitary ware of the present invention maximizes its flexibility and water repellency by including specific perfluoropolyether chains 3 on the surface of the glaze layer 2 having a unique uneven shape. . As a result, the sanitary ware of the present invention can exhibit excellent sliding resistance and maintain antifouling properties.

In the sanitary ware of the present invention, the specific perfluoropolyether chains 3 described above are highly flexible, so that the perfluoropolyether chains 3 can follow the uneven shape inherent to the surface of the glaze layer 2. . This indicates that the sanitary ware of the present invention is not only excellent in sliding resistance but also excellent in alkali resistance. Normally, even if a certain kind of coating film provided on the surface of the glaze layer itself has alkali resistance, the glaze layer will dissolve when the alkali component permeates the glaze layer, and as a result, the glaze layer surface will be covered. It disappears along with the coating film. However, since the highly flexible perfluoropolyether chains 3 are provided on the surface of the glaze layer, the perfluoropolyether chains 3 follow the uneven shape of the glaze layer, improving surface coverage. This makes it possible to prevent alkali components from penetrating into the glaze layer, and the alkali resistance function is maintained for a longer period of time.

In the sanitary ware of the present invention, when liquid is present on an inclined sanitary ware surface, the above-mentioned specific perfluoropolyether chains 3 are highly flexible, so that the liquid slides down. Therefore, it is thought that the liquid remaining on the inclined sanitary ware surface can be reduced. In addition, the high flexibility of the above-mentioned specific perfluoropolyether chains 3 facilitates the transfer of liquid present on the sanitary ware surface to absorbent articles such as tissue paper and cloth. Therefore, it is thought that the amount of liquid left on the surface of the sanitary ware can be reduced when wiping off the liquid adhering to the surface of the sanitary ware with a water-absorbing article.

In the sanitary ware of the present invention, when a solid that does not dissolve in water or an oily organic solvent exists on the inclined sanitary ware surface, the specific perfluoropolyether chains 3 described above exhibit high flexibility. By providing it, the sliding property of the solid is improved. As a result, even when no external force is applied, it is believed that the solids present on the sanitary ware surface having an inclination angle of several degrees with respect to the horizontal direction can be made to slide down easily. In addition, even if the solid adheres strongly to the surface of the sanitary ware to the extent that it cannot be removed without mechanical force such as rubbing, the high flexibility of the specific perfluoropolyether chain 3 allows the solid to adhere to the surface of the sanitary ware. Because of the improved slideability, it is thought that, for example, solids can be removed with much less mechanical force than when solids strongly adhere to the surface of sanitary ware that does not contain specific perfluoropolyether chains. be done. In other words, it is believed that the sanitary ware of the present invention containing specific perfluoropolyether chains 3 on the surface can remove solids while applying efficient mechanical force.

The ratio of the number of oxygen atoms to the number of carbon atoms in the perfluoropolyether chain. The ratio of the number of oxygen atoms to the number of all carbon atoms having CF bonds in the fluoropolyether chain 3 (hereinafter referred to as "O/C ratio") is preferably 0.1 or more. A higher O/C ratio is preferable because the flexibility of the perfluoropolyether chain 3 is increased. Specifically, the O/C ratio is preferably 0.2 or higher, more preferably 0.3 or higher, and even more preferably 0.4 or higher. Thereby, the perfluoropolyether chain 3 has excellent flexibility. The reason for this is considered as follows, but the present invention is not limited to this. The perfluoropolyether chain 3 contains fluorine atoms, oxygen atoms and carbon atoms, and it is believed that the fluorine atoms and oxygen atoms are bonded to the carbon atoms. In general, atoms bonded to carbon atoms are positioned at the vertices of a regular tetrahedral structure, so they can rotate freely around the carbon single bond. Therefore, it can take an infinite number of conformations. If the perfluoropolyether chain contains an ether bond, the presence of an oxygen atom between the two carbon atoms bonded to the oxygen atom of the ether bond makes it difficult for the interaction to work, and the energy due to the position of the twist there is almost no difference. Therefore, an organic chain containing an ether bond can relatively freely rotate around a carbon-oxygen single bond. For example, a perfluoropolyether chain having many ether bonds can change its shape with a higher degree of freedom than a fluoroalkylsilane compound having no ether bonds. That is, it is considered to be excellent in flexibility. The excellent flexibility possessed by the perfluoropolyether chain 3 enables the sanitary ware according to the present invention to have high durability, especially sliding resistance. A method for calculating the O/C ratio will be described later.

In the present invention, when the O/C ratio is high, the perfluoropolyether chain 3 is considered to be more flexible. Therefore, the higher the O/C ratio, the better. The height of the perfluoropolyether chain is reduced because the perfluoropolyether chain is more likely to fall sideways. As a result, water and alkali components are more likely to reach the surface of the glaze layer from the locations where the film has been worn due to load due to repeated use, and this makes it easier for water stains to adhere and film wear to occur. Therefore, the O/C ratio, which is an index of flexibility, is preferably 1.0 or less, more preferably 0.9 or less, and even more preferably 0.8 or less.

In the sanitary ware of the present invention, the specific perfluoropolyether chains 3 described above are highly flexible, so that the perfluoropolyether chains 3 can follow the uneven shape inherent to the surface of the glaze layer 2. . In addition to this high flexibility, the perfluoropolyether chain 3 in the present invention has high water repellency due to the predetermined F / (C + O) ratio etc. as described above, so that it not only has excellent sliding resistance but also , and has excellent alkali resistance. Normally, even if a certain kind of coating film provided on the surface of the glaze layer itself has alkali resistance, the glaze layer will dissolve when the alkali component permeates the glaze layer, and as a result, the glaze layer surface will be covered. It disappears along with the coating film. However, since the highly flexible perfluoropolyether chains 3 are provided on the surface of the glaze layer, the perfluoropolyether chains 3 follow the uneven shape of the glaze layer, improving surface coverage. In addition to this flexibility, the high water repellency of the perfluoropolyether chain 3 makes it possible to more effectively prevent alkali components from penetrating into the glaze layer, and the alkali resistance function is even longer. maintained for a period of time.

On the other hand, FIG. 2B shows a sanitary ware containing perfluoropolyether chains with a ratio of the number of carbon atoms having _CF3 bonds exceeding 20 at % and an O/C ratio of less than 0.1, that is, with low flexibility. shows a cross-sectional view of As shown in FIG. 2B, the perfluoropolyether chains on the surface of the glaze layer having an uneven shape cannot withstand the force applied particularly in the lateral direction, and the perfluoropolyether chains are worn out, resulting in poor sliding resistance. It is considered impossible to prepare.

ここで、ｐ，ｑ，ｒ，ｓは繰り返し単位の数、すなわち０以上の整数であり、ｐ，ｑ，ｒ，ｓの和は３～２００であり、式中の各繰り返し単位がランダムに結合した鎖でもよく、各繰り返し単位からなるそれぞれの高分子鎖同士が結合した鎖でもよい。Ｒ_ｆ１及びＲ_ｆ２はそれぞれ水素原子がフッ素原子に置換された、炭素原子を含む有機鎖を表す。また、繰り返し単位については直鎖形状のみで構成されているものや側鎖形状を含むものなどが存在するが、直鎖状のものが好ましい。 In the present invention, as the perfluoropolyether chain 3, those generally represented by the following formula 7 are preferred.

Here, p, q, r, s are the number of repeating units, that is, an integer of 0 or more, the sum of p, q, r, s is 3 to 200, and each repeating unit in the formula is randomly bonded It may be a chain in which each polymer chain composed of each repeating unit is bonded to each other. R _f1 and R _f2 each represent an organic chain containing carbon atoms in which hydrogen atoms are substituted with fluorine atoms. As for the repeating unit, there are those that are composed only of linear chains, those that include side chains, and the like, and those that are linear are preferred.

（式中、ｌ：ｍ：ｎ＝２３．２：２２．３：０．４（平均値）であり、式中の繰り返し単位はランダムに配列している。）、

（式中、ｌの平均値は２２．９である。）、

（式中、ｌの平均値は２３．２である。）、

（式中、ｌの平均値は１８である。）、

（式中、ｌの平均値は２３．４である。）。 As the perfluoropolyether chain 3, perfluoropolyether chains represented by the following formulas 8 to 12 are more preferable.

(In the formula, l:m:n=23.2:22.3:0.4 (average value), and the repeating units in the formula are arranged randomly.),

(wherein the average value of l is 22.9),

(wherein the average value of l is 23.2),

(wherein the average value of l is 18),

(wherein the average value of l is 23.4).

XPS Measurement Method for the Surface of Sanitary Ware In the present invention, the F/(C+O) ratio, the ratio of the number of carbon atoms having _CF3 bonds, and the O/C ratio are determined by measuring the surface of sanitary ware by X-ray photoelectron spectroscopy ( XPS). In addition, before the XPS measurement, it is preferable to wash the surface of the sanitary ware with a neutral detergent and a sponge, and then thoroughly rinse the sanitary ware with ultrapure water.

<Acquisition of XPS spectrum>
Spectra of C1s, F1s, and O1s can be obtained by XPS measurement under the following XPS measurement conditions using K-ALPHA (manufactured by Thermo Scientific) as an XPS device. When a plurality of samples are collectively measured, XPS measurement is preferably performed with each sample separated by at least 1 cm in order to avoid decomposition of C—F bonds due to X-ray irradiation.
XPS is a method of irradiating the sample surface with soft X-rays and capturing the photoelectrons emitted as the sample surface is ionized for energy analysis. , the obtained photoelectron peak is represented by the element symbol and the electron orbital (eg, the photoelectron peak obtained from the 1s orbital of carbon is represented as "C1s").

[XPS measurement conditions]
X-ray conditions: monochromatic AlKα rays, 30 W, 12 kV
Analysis area: 200 μmφ
Neutralization gun conditions: 0.1 V, 200 μA
Photoelectron extraction angle: 90°
Time Per Step: 50ms
Sweep: 5 times Pass energy: 55 eV
Analysis element (energy range, step size):
C1s (278-308eV, 0.01eV), F1s (679-699eV, 0.03eV), O1s (523-543eV, 0.03eV)
Inert gas species: Ar
Sputter voltage: 200V
Sputtering range: 2mm x 2mm
Sputter cycle: 1 second

In the spectrum obtained by XPS measurement of the surface of sanitary ware, the type of bonding state of carbon atoms contained in the perfluoropolyether chain 3 (hereinafter abbreviated as "bonding type of carbon atoms" or simply "bonding type" ) are identified. The types of bonds of carbon atoms contained in the perfluoropolyether chain are five types (1) to (5) shown in Table 2 below. Table 2 shows each binding energy of C1s of bond types (1) to (5). However, as the binding energy value of C1s of bond type (1), the literature value described in NIST Standard Reference Database 20, Version 4.1 (https://srdata.nist.gov/xps/) is used. The binding energy value of C1s listed in the above database is set up with a shift of 284.8 eV for the C1s binding energy value of the CC bond. Therefore, in order to match the conditions of the present XPS measurement, the binding energy value of C1s of the organic compound containing the bond type (1) is the same as the present XPS measurement conditions for the binding energy value of F1s contained in the organic compound. Correct using 688.5 eV. For example, bond type (1) is the bond contained in the reagent FOMBLIN Y in the NIST database, and the binding energy value for C1s is listed as 295.2 eV. Here, since the F1s binding energy value of FONBLIN Y is 689.1 eV, this F1s binding energy literature value is corrected to 688.5 eV. That is, the binding energy value of this F1s is shifted to the low energy side by 0.6 eV and corrected. Along with this, the binding energy value of C1s is also shifted to the lower energy side by 0.6 eV and corrected, whereby the binding energy value of C1s of bond type (1) is obtained as 294.6 eV. This value is used as the bond energy value of C1s of bond type (1).

In XPS, the bond energy of the photoelectrons obtained from the central atom changes greatly depending on the bonding state between the target atom (also called "central atom") and the surrounding atoms (also called "neighboring atoms") (that is, chemical shift). Therefore, it is possible to specify which peak corresponds to which bond type in the XPS spectrum obtained from the binding energy of C1s of bond types (1) to (5), that is, peak separation. Become.

One factor of chemical shift is the difference in electronegativity of neighboring atoms. Between the central atom (carbon atom in the present invention) and neighboring atoms (fluorine atom, oxygen atom, carbon atom in the present invention), the more neighboring atoms with high electronegativity exist around the central atom. A charge bias occurs at . As a result, the binding energy of photoelectrons obtained from the central atom (the binding energy of C1s in the present invention) shifts to the higher side. The constituent atoms of the perfluoropolyether chain are fluorine atoms, oxygen atoms, and carbon atoms in order of increasing electronegativity. The binding energy becomes higher. In addition, the binding energy of C1s becomes lower in the order in which the neighboring atoms are an oxygen atom and a carbon atom. Based on this premise, when the bond types (1) to (5) are arranged in descending order of C1s bond energy, (1)>(2)>(3)>(4)>(5). All of the bond types (1) to (5) appear in the spectrum in the C1s bond energy region (289 eV to 298 eV), which is higher than the band band of carbon (around 285 eV).

In the obtained XPS spectrum, first, the influence of the peak derived from potassium on the C1s spectrum is confirmed. When the base and/or glaze layers for sanitary ware contain potassium, there may generally be a K2p _1/2 peak in the region of 296.8±1.0 eV. However, depending on the height of the perfluoropolyether chains present on the surface of the glaze layer, even if the substrate for sanitary ware and/or the glaze layer contains potassium, Sometimes the K2p _1/2 peak is not seen. In this case, the following peak separation can be performed on the assumption that the C1s spectrum is not affected by the peak derived from potassium.

If a K2p _1/2 peak is observed in the region of 296.8±1.0 eV in the spectrum of C1s, the following is considered as having an effect of potassium on the spectrum of C1s. Potassium-derived peaks that affect the spectrum of C1s are derived from two types of electron orbitals, K2p _1/2 and K2p _3/2 . In general, the peak of K2p _3/2 has a photoelectron binding energy value 2.8 eV lower than that of K2p _1/2 , and its peak area is twice that of K2p _1/2 . The K2p _3/2 peak is located at 294.0±1.0 eV, which overlaps with the peaks from perfluoropolyether chains of bond types (2) and (3) listed in Table 2. Therefore, it is difficult to confirm the existence of the K2p3 _/2 peak from the peak shape. However, the K2p _1/2 peak is detected as a single peak in the photoelectron binding energy region separated from the peak derived from the perfluoropolyether chain. Therefore, when the presence of a K2p _1/2 peak is confirmed, it is determined that a K2p _3/2 peak exists, and from the binding energy of K2p _1/2 and its peak area, the binding of K2p _3/2 It is possible to calculate the energy and its peak area. Assuming that the calculated K2p _3/2 peak exists in the C1s spectrum, this peak area is taken into consideration when separating the peaks of the C1s spectrum, and the peaks are separated by removing the influence of the peak derived from potassium. Therefore, even when the spectrum of C1s is affected by a peak derived from potassium, it is possible to calculate the composition ratio of each type of bond contained in the perfluoropolyether chain.

<Peak Separation>
The obtained spectrum is subjected to peak separation using data analysis software Avantage (Version 5, manufactured by Thermo Scientific). Peak separation is to separate the detected peaks from the overall waveform of the obtained spectrum, and specify the bonding state corresponding to each obtained waveform. This peak separation makes it possible to calculate the ratio of different bonding states contained in the perfluoropolyether chain, even though the elements are the same element (carbon atoms in the present invention). Details of the method of peak separation are described below. First, in the obtained F1s spectrum, the peak positions of the C1s, F1s, and O1s measured so that the F1s binding energy of the peak derived from the fluorine atom that binds to the carbon atom is 688.5 eV in the entire binding energy range. correct. In this state, the photoelectron spectra of bond types (1) to (5) present in the C1s spectrum are subjected to peak separation. A specific method for C1s peak separation will be described below. First, the peak background is removed by the Shirley method in the range of 278 eV (starting point) to 300 eV (ending point) in the measurement range of C1s. However, for the start and end points, the background intensity at that point is the average value of the intensity within a range of ±0.25 eV with each point as the median. For example, at the C1s start point of 278 eV, the average value of the intensity in the range of ±0.25 eV from the median value of 278 eV, ie, the range of 277.75 eV to 278.25 eV, is taken as the background intensity at the start point. After that, the 285 eV peak in the C1s bond energy is a C—C bond or C—H bond, the 286 eV peak in the C1s bond energy is a C—O bond, and the bond types (1) to (5) described in Table 2 The C1s binding energy peak is assigned to each bond type, the 296.8±1.0 eV peak in the C1s binding energy is assigned as K2p _1/2 , and additional peaks are added. In addition, peaks proposed on the software are also added as necessary. The peak shape to be added follows the Gauss-Lorentz distribution. After that, fitting is performed using the following peak fitting conditions to obtain the spectrum of each binding type. If the fitting result does not satisfy the following fitting completion criteria, add one peak at the position of the binding energy of C1s that takes the maximum value among the positive maxima in the second derivative spectrum displayed on the screen, Perform fitting again using the following peak fitting conditions. This operation is performed until the following fitting completion judgment criteria are met, and once the fitting is completed. Subsequently, if a K2p _1/2 peak is observed in the range of 296.8±1.0 eV, the effect of the potassium peak is removed by the following procedure. First, the numerical values of the K2p _1/2 binding energy, peak height and full width at half maximum (FWHM) determined by the above fitting are specified on the software. At this time, the binding energy of K2p _3/2 is smaller than the binding energy of K2p _1/2 by 2.8 eV, and the half width of K2p _3/2 is equal to K2p _1/2 , and numerical values are specified on the software. Furthermore, the peak height is adjusted on the software so that the peak area of K2p _3/2 is 1.95 to 2.05 times the peak area of K2p _1/2 . After that, by performing fitting again using the following peak fitting conditions, a spectrum of each bond type in consideration of the potassium peak is obtained. Thus, XPS peak separation is completed.
[Peak fitting conditions]
Fitting Algorithm: Powell
Maximum Iterations: 500
Convergence: 1e-05
Gauss-Lorentz Mix: Product
[Fitting Completion Criteria]
Normalized Chi Square ≤ 10.0

<Calculation of Composition Ratio of Bond Types of Carbon Atoms Contained in Perfluoropolyether Chain>
From the spectra of bond types (1) to (5) identified by XPS peak separation, data analysis software Avantage (Version 5, manufactured by Thermo Scientific) is used to calculate the composition ratio of bond types (1) to (5). .
The ratio of the peak area intensity of each bond type (1) to (5) with respect to the sum of the peak area intensities (Area Intensities) of the spectra of each bond type (1) to (5) obtained by peak separation, It is defined as the composition ratio of each bond type (1) to (5) in the perfluoropolyether chain, and is calculated in units of at %.

<Calculation of F / (C + O) ratio>
From the compositional ratio of bond types (1) to (5) obtained by peak separation, the F/(C+O) ratio contained in the perfluoropolyether chain is obtained. Since it is not possible to directly determine the number of carbon atoms, the number of oxygen atoms, and the number of fluorine atoms contained in the perfluoropolyether chain from the calculated composition ratio of the bond types (1) to (5), F/ (C+O) ratio is calculated by the following method. Assuming that the number of carbon atoms contained in the perfluoropolyether chain is 100, the composition ratio of carbon atoms of each of the bond types (1) to (5) is also considered as the number of carbon atoms. Since the types of atoms bonded to each of the bond types (1) to (5) are fixed, the number of oxygen atoms and the number of fluorine atoms can be obtained when the number of carbon atoms in the perfluoropolyether chain is 100. can be done. Thereby, the F/(C+O) ratio can be obtained.

For example, as bond types contained in the perfluoropolyether chain in the compound represented by the above formula (a), (2), (4), and (5) were detected, and the composition ratio of each was 34.0 at. %, 56.0 at %, and 10.0 at %, the following conditions:
・ When C is bonded to the carbon atom of the central atom, this C is not counted in the number of carbon atoms ・ When O is bonded to the carbon atom of the central atom, this O is counted as 1/2 ・When F is bonded to the carbon atom of the central atom, this F is counted as one, and the number of carbon atoms is 34.0 for bond type (2) and 34.0 for bond type (4). 56.0 and 10.0 for bond type (5), totaling 100, and the number of oxygen atoms is 34.0 × 2 × 1/2 for bond type (2), 56.0×1×1/2 for bond type (4) and 10.0×0×1/2 for bond type (5), for a total of 62.0. The number of fluorine atoms is 34.0×2×1 for bond type (2), 56.0×2×1 for bond type (4), and 10 for bond type (5). .0×2×1 for a total of 200.0. Therefore, the F/(C+O) ratio is calculated as 1.23. The F/(C+O) ratio of the present invention is obtained by rounding off the calculated F/(C+O) ratio to the second decimal place.

<Calculation of the ratio of the number of carbon atoms having a _CF3 bond to the number of carbon atoms having a CF bond>
In the present invention, when the composition ratio of bond type (3) obtained by peak separation is high, that is, exceeds 20 at %, it means that the perfluoropolyether chain has bond type (3). This means that the perfluoropolyether backbone likely has side chains (--CF ₃ ).

<Calculation of O/C ratio>
From the composition ratio of bond types (1) to (5) obtained by peak separation, the O/C ratio contained in the perfluoropolyether chain is obtained. Since it is not possible to directly determine the number of carbon atoms and the number of oxygen atoms contained in the perfluoropolyether chain from the calculated composition ratio of the bond types (1) to (5), the O / C ratio is calculated by the following method. Calculated by Assuming that the number of carbon atoms contained in the perfluoropolyether chain is 100, the composition ratio of carbon atoms of each of the bond types (1) to (5) is also considered as the number of carbon atoms. Since the types of atoms bonded to each of the bond types (1) to (5) are fixed, the number of oxygen atoms can be determined when the number of carbon atoms in the perfluoropolyether chain is 100. Thereby, the O/C ratio can be obtained.

For example, as bond types contained in the perfluoropolyether chain in the compound represented by the above formula (a), (2), (4), and (5) were detected, and the composition ratio of each was 34.0 at. %, 56.0 at %, and 10.0 at %, the following conditions:
・ When C is bonded to the carbon atom of the central atom, this C is not counted in the number of carbon atoms ・ When O is bonded to the carbon atom of the central atom, this O is counted as 1/2 according to , the number of carbon atoms is 34.0 for bond type (2), 56.0 for bond type (4), and 10.0 for bond type (5), totaling 100. , and the number of oxygen atoms is 34.0 × 2 × 1/2 for bond type (2), 56.0 × 1 × 1/2 for bond type (4), and 5 ) is 10.0×0×1/2 for a total of 62.0. Therefore, the O/C ratio is calculated as 0.62. The O/C ratio of the present invention is obtained by rounding off the calculated O/C ratio to the second decimal place.

Sputtering time by XPS depth direction analysis of the sanitary ware surface In the present invention, in the profile obtained by the XPS depth direction analysis described later, the XPS measurement point of the sanitary ware surface is set as the starting point, and the fluorine atom peak at this starting point _{1.0 at _} % or less is preferably 60 seconds or less. In the present invention, the height of the perfluoropolyether chains 3 contained in the surface of the glaze layer can be specified using the sputtering time as an index obtained by XPS depth direction analysis of the sanitary ware surface.

The sputtering time of the sanitary ware surface by XPS depth direction analysis can be confirmed by depth direction analysis by combined use of XPS measurement and sputtering using Ar ions. Depth profile analysis by combined use of this XPS measurement and sputtering using Ar ions is referred to as “XPS depth profile analysis”. In the XPS depth direction analysis, the surface of the sanitary ware is first washed with a neutral detergent, rinsed with ultrapure water, and blown off with air. When a plurality of samples are collectively measured, XPS measurement is preferably performed with each sample separated by at least 1 cm in order to avoid decomposition of C—F bonds due to X-ray irradiation. After that, the XPS measurement of the sanitary ware surface is performed, and then the sputtering using Ar ions and the XPS measurement are alternately repeated. The above-mentioned "XPS measurement conditions" can be used as the conditions for XPS measurement. The following conditions can be used for sputtering conditions (hereinafter also referred to as “sputtering conditions”). An XPS measurement is performed for each "sputter cycle" of the sputtering conditions. Depth profile analysis of XPS provides spectral information.

[Sputtering conditions]
Inert gas species: Ar
Sputter voltage: 200V
Sputtering range: 2mm x 2mm
Sputtering cycle: 1 second Note that the sputtering voltage refers to the voltage applied to the Ar ion gun, and the sputtering range refers to the range of the surface to be scraped by sputtering. Moreover, the sputtering cycle refers to the time during which Ar gas is continuously irradiated for each measurement in the depth direction, and the sum of the sputtering cycles is the sputtering time.

In the profile obtained by XPS depth direction analysis, the XPS measurement point of the sanitary ware surface (that is, perfluoropolyether chain) is the starting point, and the fluorine atom peak area (A _s ) at this starting point is The end point is the point at which the ratio of the absolute value of the difference between the peak area of fluorine atoms (A _a ) and the peak area of fluorine atoms (A _b ) at the previous measurement point is 1.0 atomic % or less.
End point: |A _b −A _a |/A _s ≦0.01

The sputtering time from the start point to the end point described above can be used as an indicator of the height of the perfluoropolyether chains.

In the present invention, the sputtering time from the start point to the end point is preferably within 60 seconds, more preferably within 30 seconds, and even more preferably within 20 seconds. Also, the lower limit of the sputtering time is preferably 5 seconds or longer. A suitable range of the sputtering time may be an appropriate combination of the above upper limit and lower limit.

In the sanitary ware according to the present invention, it is preferable that a large number of perfluoropolyether chains 3 are formed in the form of a film or layer on the surface of the glaze layer 2 . The membrane containing perfluoropolyether chains 3 is preferably a thin film. When the perfluoropolyether chain 3 is formed in a film or layer, in the profile obtained by the XPS depth direction analysis described above, the XPS measurement point on the sanitary ware surface is set as the starting point, and fluorine atoms at this starting point The ratio of the absolute value of _the difference between the fluorine atom peak area (A _a ) at a certain measurement point and the fluorine atom peak area (A _b ) at the previous measurement point to the peak area (A s ) of 1 The sputtering time to the end point of 0.0 at % or less can be used as an index of the thickness of the film or layer.

When the perfluoropolyether chain 3 is film-like or layer-like, its height is preferably 1 nm or more and 10 nm or less, more preferably 1 nm or more and 5 nm or less.

The perfluoropolyether chains contained in the surface of the sanitary ware of the present invention may contain two or more types of perfluoropolyether chains, or may contain a single type of perfluoropolyether chain.

The surface of the sanitary ware of the present invention may contain not only perfluoropolyether chains but also fluoroalkyl chains. Specifically, the content of the fluoroalkyl chain is preferably less than 50 at%, more preferably 30 at% or less, more preferably 10 at. % or less is even more preferred.

The invention is further illustrated by the following examples. However, the present invention is not limited to these examples.

1. Production of sanitary ware
1-1. Preparation of base material for sanitary ware and glaze layer <Production of base material for sanitary ware>
A slurry for sanitary ware prepared from raw materials such as silica sand, feldspar, limestone and clay was cast in a gypsum mold to obtain a compact. The molded body was dried. The "base material for sanitary ware" is obtained by firing the dried compact in the firing step described later.

<Preparation of glaze>
A plurality of glaze raw materials having compositions shown in Table 3 below in terms of oxides were prepared. 600 g of each glaze raw material, 400 g of water and 1 kg of alumina balls were placed in a ceramic pot having a volume of 2 liters and pulverized with a ball mill for about 65 hours to obtain a glaze.

A glaze was applied onto the dried molded body by a spray coating method, and fired at 1100 to 1200° C. to prepare a substrate for sanitary ware on which a glaze layer was formed. The surface of the obtained glaze layer was processed as necessary to prepare substrates A to F having arithmetic mean linear roughness Ra shown in Table 4 below. The arithmetic mean line roughness Ra is measured according to JIS-B0633 (2001) "7. Method and procedure for evaluation by a stylus type surface roughness measuring instrument", It was measured using a needle-type surface roughness measuring device. The color of each glaze layer is mainly based on the pigment. Base material A is obtained by applying a glaze having the composition shown in Table 3 to a base material for sanitary ware, then applying a glaze having a composition shown in Table 3 excluding ZrO and pigments, and firing to form a glaze layer. It is formed. Base material B is obtained by applying a glaze having the composition shown in Table 3 to a base material for sanitary ware and firing to form a glaze layer. For the base material C, non-spherical alumina particles are used as an abrasive for the base material A, the particle size range of the abrasive is selected from 1 μm to 100 μm, the compressed air supply pressure, the projection distance, the projection angle, and the projection time was obtained by appropriately selecting and wet blasting. Substrate D is a sanitary ware substrate coated with a glaze containing 1 to 10 wt% excess alkaline earth metal oxide in the composition shown in Table 3 and fired to form a glaze layer. be. Base material E uses an abrasive material of particle size #150 (median particle size 63 to 106 μm): Fujirandom A (manufactured by Fuji Seisakusho Co., Ltd.) for base material A, a compressor pressure of 0.6 MPa, and a nozzle diameter of 5 mm. It is obtained by dry blasting under the conditions. Substrate F is an abrasive material with a particle size of #150 (median particle size 63 to 106 μm): Fujirandom A (manufactured by Fuji Seisakusho Co., Ltd.), a compressor pressure of 0.3 MPa, and a nozzle diameter of 5 mm. It is obtained by dry blasting under the conditions.

1-2. In order to remove stains present on the surface of the pretreated glaze layer and to activate hydroxyl groups present on the surface, pretreatment 1 or 2, which will be described later, was performed.

<Pretreatment 1>
First, the surface of the glaze layer was washed with a commercially available sponge i soaked in a neutral detergent (product name: Clean Ace, manufactured by AS ONE). Next, a small amount of ceria powder (manufactured by Treibacher Industrie AG) was sprinkled on the surface of the glaze layer and washed with a commercially available sponge ii. Next, while applying running water to the surface of the glaze layer, the remaining ceria powder was removed with a commercially available sponge iii, and ultrapure water was applied to wash it (spongees i, ii, and iii are different, and each used).
After that, the glaze layer was immersed in an aqueous solution containing an alkaline detergent (product name: Semi-clean, manufactured by Yokohama Yushi Kogyo Co., Ltd.) whose concentration was adjusted to 5 wt % with deionized water, and ultrasonically cleaned for 5 minutes. Next, ultrapure water was applied to the surface of the glaze layer to remove the alkaline detergent. Further, the glaze layer was immersed in ultrapure water and ultrasonically cleaned for 5 minutes. Next, ultrapure water was again applied to the surface of the glaze layer, and water was removed with an air duster.

<Pretreatment 2>
First, the surface of the glaze layer was washed with a commercially available sponge i soaked in a neutral detergent (product name: Clean Ace, manufactured by AS ONE). Then, running water was applied to the surface of the glaze layer to remove the neutral detergent.
After that, the glaze layer was immersed in an aqueous solution containing an alkaline detergent (product name: Semi-clean, manufactured by Yokohama Yushi Kogyo Co., Ltd.) whose concentration was adjusted to 5 wt % with deionized water, and ultrasonically cleaned for 5 minutes. Next, ultrapure water was applied to the surface of the glaze layer to remove the alkaline detergent. Further, the glaze layer was immersed in ultrapure water and ultrasonically cleaned for 5 minutes. Next, ultrapure water was again applied to the surface of the glaze layer, and water was removed with an air duster.

1-3. Formation of perfluoropolyether chain <Preparation of reagent>
The following reagents a to g containing compounds containing perfluoropolyether chains or compounds containing fluoroalkyl chains were prepared. In all of reagents a to g, partial structures containing fluorine-bonded carbon atoms are specified. In the structural formula of the active ingredient contained in each reagent, X _Si means a combination of an organic group containing at least one Si atom and the Si atom containing no fluorine atom and a hydroxyl group or a hydrolyzable group. do. A hydrolyzable group means an alkoxy group and a halogeno group. Specifically, they are -OCH ₃ , -OCH ₂ CH ₃ and -Cl.

（式中、ｌ：ｍ：ｎ＝２３．２：２２．３：０．４（平均値）であり、Ｘ_Ｓｉは、Ｓｉ原子を平均３．０個含み、Ｓｉ原子にフッ素原子を含まない有機基と、水酸基または加水分解可能な基とが結合したものを意味する。加水分解可能な基とは、アルコキシ基、ハロゲノ基を意味する。具体的には、－ＯＣＨ_３、－ＯＣＨ_２ＣＨ_３、－Ｃｌである。なお、式中の繰り返し単位はランダムに配列している。これらの値はＮＭＲにより試薬ａを液分析して求めた。パーフルオロポリエーテル鎖の数平均分子量は、^１９Ｆ－ＮＭＲの結果から、またＸ_Ｓｉの存在は^１Ｈ－ＮＭＲおよび^２９Ｓｉ－ＮＭＲの検出スペクトルから確認した。） Reagent a : a reagent consisting of the following components and containing a compound containing a perfluoropolyether chain represented by formula (a) as an active ingredient

(In the formula, l: m: n = 23.2: 22.3: 0.4 (average value), X _Si contains an average of 3.0 Si atoms, and Si atoms do not contain fluorine atoms It means a combination of an organic group and a hydroxyl group or a hydrolyzable group.The hydrolyzable group means an alkoxy group or a halogeno group.Specifically, _--OCH.sub.3 , _{--OCH.sub.2CH} . ₃ and -Cl.The repeating units in the formula are arranged randomly.These values were obtained by liquid analysis of reagent a by NMR.The number average molecular weight of the perfluoropolyether chain is ¹⁹ . The presence of X _Si was confirmed from the results of F-NMR and from the detection spectra of ¹ H-NMR and ²⁹ Si-NMR.)

(component)
・Fluoroalkyl ether (CAS No.163702-06-4) 30-40%
・Fluoroalkyl ether (CAS No.163702-06-5) 40-50%
・Compound containing perfluoropolyether chain of formula (a) (active ingredient) 10-20%

（式中、ｌの平均値は２２．９である。Ｘ_ＳｉはＳｉ原子を平均２．０個含む以外は式（ａ）のＸ_Ｓｉと同様である。これらの値はＮＭＲにより試薬ｂを液分析して求めた。パーフルオロポリエーテル鎖の数平均分子量は、^１９Ｆ－ＮＭＲの結果から、またＸ_Ｓｉの存在は^１Ｈ－ＮＭＲおよび^２９Ｓｉ－ＮＭＲの検出スペクトルから確認した。）） Reagent b : a reagent consisting of the following components and containing a compound containing a perfluoropolyether chain represented by formula (b) as an active ingredient

(In the formula, the average value of l is 22.9. X _Si is the same as X _Si of formula (a) except that it contains an average of 2.0 Si atoms. These values were determined by NMR using reagent b. The number average molecular weight of the perfluoropolyether chain was confirmed from the results of ¹⁹ F-NMR, and the presence of X _Si was confirmed from the detection spectra of ¹ H-NMR and ²⁹ Si-NMR.))

(component)
・Ethyl nonafluorobutyl ether (CAS No.163702-05-4) 25-35%
・Ethyl nonafluoroisobutyl ether (CAS No.163702-06-5) 45-55%
・Compound containing perfluoropolyether chain of formula (b) (active ingredient) 15-25%

（式中、ｌの平均値は２３．２である。Ｘ_ＳｉはＳｉ原子を平均３．７個含む以外は式（ａ）のＸ_Ｓｉと同様である。これらの値はＮＭＲにより試薬ｃを液分析して求めた。パーフルオロポリエーテル鎖の数平均分子量は、^１９Ｆ－ＮＭＲの結果から、またＸ_Ｓｉの存在は^１Ｈ－ＮＭＲおよび^２９Ｓｉ－ＮＭＲの検出スペクトルから確認した。） Reagent c : a reagent consisting of the following components and containing a compound containing a perfluoropolyether chain represented by formula (c) as an active ingredient

(In the formula, the average value of l is 23.2. X _Si is the same as X _Si of formula (a) except that it contains an average of 3.7 Si atoms. The number average molecular weight of the perfluoropolyether chain was confirmed from the results of ¹⁹ F-NMR, and the presence of X _Si was confirmed from the detection spectra of ¹ H-NMR and ²⁹ Si-NMR.)

(component)
・Ethyl nonafluorobutyl ether (CAS No.163702-05-4) 25-35%
・Ethyl nonafluoroisobutyl ether (CAS No.163702-06-5) 45-55%
・Compound containing perfluoropolyether chain of formula (c) (active ingredient) 15-25%

（式中、ｌの平均値は１８であり、この値はＮＭＲにより試薬ｄを液分析して求めた。パーフルオロポリエーテル鎖の数平均分子量は、^１９Ｆ－ＮＭＲの結果から確認した。また、Ｘ_ＳｉはＳｉ原子を平均５．０個含む以外は式（ａ）のＸ_Ｓｉと同様である。） Reagent d : a reagent consisting of the following components and containing a compound containing a perfluoropolyether chain represented by formula (d) as an active ingredient

(In the formula, the average value of l is 18, and this value was obtained by liquid analysis of reagent d by NMR. The number average molecular weight of the perfluoropolyether chain was confirmed from the results of ¹⁹ F-NMR. , X _Si is the same as X _Si of formula (a) except that it contains 5.0 Si atoms on average.)

(component)
・1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane (CAS No.80793-17-5)
99.5% or more ・Perfluoropolyether chain-containing silane compound of formula (d) (active ingredient) less than 0.5%

（式中、ｌの平均値は２３．４であり、この値はＮＭＲにより試薬ｅを液分析して求めた。パーフルオロポリエーテル鎖の数平均分子量は、^１９Ｆ－ＮＭＲの結果から確認した。また、Ｘ_ＳｉはＳｉ原子を平均３．０個含む以外は式（ａ）のＸ_Ｓｉと同様である。） Reagent e : a reagent consisting of the following components and containing a compound containing a perfluoropolyether chain represented by formula (e) as an active ingredient

(In the formula, the average value of l is 23.4, and this value was obtained by liquid analysis of reagent e by NMR. The number average molecular weight of the perfluoropolyether chain was confirmed from the results of ¹⁹ F-NMR. Also, X _Si is the same as X _Si of formula (a) except that it contains 3.0 Si atoms on average.)

(component)
・Ethyl nonafluorobutyl ether (CAS No.163702-05-4) 25-35%
・Ethyl nonafluoroisobutyl ether (CAS No.163702-06-5) 45-55%
・Compound containing perfluoropolyether chain of formula (e) (active ingredient) 15-25%

（式中、Ｘ_ＳｉはＳｉ原子を平均１．０個含む以外は式（ａ）のＸ_Ｓｉと同様である。） Reagent f : A reagent consisting of the following components and having as an active ingredient a compound containing a perfluoropolyether chain (including a _CF3 side chain) represented by formula (f)

(In the formula, X _Si is the same as X _Si in formula (a) except that it contains an average of 1.0 Si atoms.)

(component)
・Fluoroalkyl ether 80-85%
・Compound containing perfluoropolyether chain of formula (f) (including _CF3 side chain) (active ingredient) 15-20%

（式中、Ｘ_ＳｉはＳｉ原子を平均１．０個含む以外は式（ａ）のＸ_Ｓｉと同様である。） Reagent g : a reagent containing a compound containing a fluoroalkyl chain represented by formula (g) as an active ingredient

(In the formula, X _Si is the same as X _Si in formula (a) except that it contains an average of 1.0 Si atoms.)

(component)
・Compound containing fluoroalkyl chain of formula (g) (active ingredient, CAS No.83048-65-1)>98.0%

<Preparation of treatment liquid>
206 μL of reagent a was added dropwise to 30 g of a fluorine solvent (product name: NOVEC7200, manufactured by 3M) and lightly stirred to obtain treatment liquid a in which the concentration of the active ingredient of reagent a was about 0.1 wt %. By the same method, treatment liquids b, c, e, f and g containing reagents b, c, e, f and g were obtained. Since the concentration of the active ingredient in the reagent d was 0.1 wt %, the reagent d was used as the treatment liquid d without being diluted with a fluorine solvent.

<Application of treatment liquid>
Using a spray gun, the surface of substrate A subjected to pretreatment 1 was coated with treatment liquid a at a pressure of 0.04 MPa, allowed to stand for 30 seconds, and thermally dried in a drying oven at 120° C. for 30 minutes. After that, the sanitary ware of Example 1 was obtained by curing for 3 hours in a constant temperature and humidity bath set at a temperature of 80° C. and a humidity of 80% and at room temperature and atmospheric pressure for 17 hours.
In the same manner, sanitary wares of Examples 2 to 15 and Comparative Examples 1 to 10 were obtained using substrates A to F pretreated and each treatment solution shown in Table 7 below.

2. Analysis/Evaluation The sanitary wares (Examples 1 to 15 and Comparative Examples 1 to 10) produced as described above were subjected to the following analysis/evaluation.

2-1. XPS Analysis For the sanitary wares of Examples 1-5 and Comparative Examples 1-2, the surface of each sanitary ware was measured by X-ray photoelectron spectroscopy (XPS). Before measurement, the surface of each sanitary ware was washed with a neutral detergent and a sponge, and then thoroughly rinsed with ultrapure water.

Using K-ALPHA (manufactured by Thermo Scientific) as an XPS device, the surface of each sanitary ware was measured under the following "XPS measurement conditions" to obtain C1s, F1s, and O1s spectra. It is obvious that the structure of the compound formed is the same if the treatment method with the treatment liquid is the same, and this analysis result is an analysis result showing the structure of the compound itself regardless of the pretreatment method. can be interpreted.

[XPS measurement conditions]
X-ray conditions: monochromatic AlKα rays, 30 W, 12 kV
Analysis area: 200 μmφ
Neutralization gun conditions: 0.1 V, 200 μA
Photoelectron extraction angle: 90°
Time Per Step: 50ms
Sweep: 5 times Pass energy: 55 eV
Analysis element (energy range, step size):
C1s (278-308eV, 0.01eV), F1s (679-699eV, 0.03eV), O1s (523-543eV, 0.03eV)
Inert gas species: Ar
Sputter voltage: 200V
Sputtering range: 2mm x 2mm
Sputter cycle: 1 second

The type of bond state of carbon atoms contained in the perfluoropolyether chain or fluoroalkyl chain contained in the surface of each sanitary ware (hereinafter simply referred to as "bond type") is shown in Table 5 below (1) to (7) seven. The binding energies of C1s for each of the bond types (1) to (7) are shown in Table 5 below. However, the binding energy value of C1s of the bond type with * (hereinafter referred to as "bond type *") is the value obtained by correcting the literature value described in NIST Standard Reference Database 20, Version 4.1 as follows. was used. The binding energy value of C1s described in the above database is set up by shifting the binding energy value of C1s of the C--C bond to 284.8 eV. Therefore, in order to match the conditions of this XPS measurement, the binding energy value of C1s of the organic compound containing the bond type * and the binding energy value of F1s contained in the organic compound were set under the same conditions as this XPS measurement condition. Corrected using 5 eV.

<Peak Separation>
The obtained spectrum was subjected to peak separation using data analysis software Avantage (Version 5, manufactured by Thermo Scientific).
First, in the obtained F1s spectrum, the peak positions of the C1s, F1s, and O1s measured so that the F1s binding energy of the peak derived from the fluorine atom that binds to the carbon atom is 688.5 eV in the entire binding energy range. corrected. In this state, peak separation was performed for the photoelectron spectra of bond types (1) to (7) present in the spectrum of C1s. A specific method for C1s peak separation will be described below. First, the peak background was removed by the Shirley method in the range of 278 eV (start point) to 300 eV (end point) in the measurement range of C1s. However, for the starting point and the ending point, the average value of the intensity within the range of ±0.25 eV with each point as the median value was taken as the background intensity at that point. For example, at the starting point of C1s of 278 eV, the average value of the intensity in the range of ±0.25 eV of the median value of 278 eV, ie, the range of 277.75 eV to 278.25 eV, was taken as the starting background intensity. After that, the 285 eV peak in the C1s bond energy is a C—C bond or C—H bond, the 286 eV peak in the C1s bond energy is a C—O bond, and the bond types (1) to (7) described in Table 5 The C1s binding energy peak was assigned to each bond type, and the 296.8±1.0 eV peak in the C1s binding energy was assigned as K2p _1/2 , respectively, and additional peaks were added. Other peaks suggested on the software were also added as needed. The added peak was assumed to follow the Gauss-Lorentz distribution in peak shape. After that, by performing fitting using the following peak fitting conditions, the spectrum of each binding type was obtained. If the fitting result does not satisfy the following fitting completion criteria, add one peak at the position of the binding energy of C1s that takes the maximum value among the positive maxima in the second derivative spectrum displayed on the screen, Fitting was performed again using the following peak fitting conditions. This operation was performed until the fitting completion judgment criteria below were satisfied, and the fitting was completed once. Subsequently, for the treatment liquids a, b, d, e, f, and g in which the K2p _1/2 peak was confirmed in the range of 296.8 ± 1.0 eV, the influence of the potassium peak was removed by the following procedure. . First, the numerical values of the K2p _1/2 binding energy, peak height and half maximum width (FWHM) determined by the above fitting were specified on the software. At this time, the binding energy of K2p _3/2 was 2.8 eV smaller than the binding energy of K2p _1/2 , and the half width of K2p _3/2 was equal to K2p _1/2 , and numerical values were specified on the software. Furthermore, the peak height was adjusted on the software so that the peak area of K2p _3/2 was 1.95 to 2.05 times the peak area of K2p _1/2 . After that, fitting was performed again using the following peak fitting conditions to obtain a spectrum of each bond type in consideration of the potassium peak. From the above, XPS peak separation was completed.
[Peak fitting conditions]
Fitting Algorithm: Powell
Maximum Iterations: 500
Convergence: 1e-05
Gauss-Lorentz Mix: Product
[Fitting Completion Criteria]
Normalized Chi Square ≤ 10.0

3 to 9 show the XPS spectrum of the surface of each sanitary ware and the results of peak separation.

<Calculation of Composition Ratio of Bond Types of Carbon Atoms Contained in Perfluoropolyether Chain or Fluoroalkyl Chain>
From the spectra of bond types (1) to (7) identified by peak separation, the composition ratios of bond types (1) to (7) were calculated using data analysis software Avantage (Version 5, manufactured by Thermo Scientific). Specifically, the peak area of the spectrum of each bond type (1) to (7) with respect to the sum of the peak area intensities of all the spectra of bond types (1) to (7) obtained by XPS measurement and peak separation The ratio of strength was defined as the composition ratio of each bond type (1) to (7) in the perfluoropolyether chain or fluoroalkyl chain, and was calculated in units of at %. Table 6 shows the results.

<Calculation of the ratio of the number of carbon atoms having a _CF3 bond to the number of carbon atoms having a CF bond>
The composition ratio of bond type (3) in the perfluoropolyether chain was calculated. The results obtained are shown in Table 7 below.

<Calculation of F / (C + O) ratio>
From the composition ratio of bond types (1) to (7) obtained by peak separation, the F/(C+O) ratio of the perfluoropolyether chain or fluoroalkyl chain was calculated using the method already described. The results are shown in Table 7 below.

<Calculation of O/C ratio>
From the composition ratio of bond types (1) to (7) obtained by peak separation, the O/C ratio of the perfluoropolyether chain or fluoroalkyl chain was calculated using the method already described. The results are shown in Table 7 below.

2-2. Confirmation of Sputtering Time by XPS Depth Direction Analysis of Sanitary Ware Surface The surface of sanitary ware was subjected to XPS depth direction analysis. After the XPS measurement of the sanitary ware surface, sputtering using Ar ions and XPS measurement were alternately repeated using the above-described "XPS measurement conditions" and "sputtering conditions". XPS measurements were performed for each “sputter cycle” of the sputtering conditions. Spectral information was obtained by XPS depth profiling. With the XPS measurement point on the surface of each sanitary ware as the starting point, the peak area (A _{a ) of the fluorine atom at a certain measurement point with respect to the peak area (A s )} of the fluorine atom at this starting point and the fluorine at the measurement point one point before that point The point at which the ratio of the absolute value of the difference from the atomic peak area (A _b ) was 1.0 at % or less was defined as the end point, and the sputtering time from the start point to the end point was determined. Table 7 shows the results.

2-3. Evaluation of Scale Cleanability Each sanitary ware was evaluated for scale cleanability after Durability Test 1 or Durability Test 2 below.

Durability test 1: Sliding test 1 to 2 mL of deionized water is dropped on the sanitary ware surface, and the non-woven fabric portion of a sponge (Scotch-Brite (registered trademark) hybrid bonded sponge, manufactured by 3M Japan) is placed on the surface with a load of 50 g/cm ² . After pressing, the sponge was reciprocated 20,000 times.

Durability Test 2: Sliding Test after Alkali Immersion Each sanitary ware was immersed in an alkaline cleaning agent (Kabikiller, manufactured by Johnson Co., Ltd.) maintained at 40° C. for 16 hours. After that, the sanitary ware was taken out, and running water was applied to it, and then ultrapure water was applied to it, and the water was blown off with an air duster. Next, the durability test 1 (sliding test) described above was performed.

Durability Test 3: Sliding Test after Alkali Immersion Each sanitary ware was immersed in an alkaline cleaning agent (Kabikiller, manufactured by Johnson Co., Ltd.) maintained at 25° C. for 1.6 hours. After that, each sanitary ware was taken out, and was hit with running water, followed by ultrapure water, and dried with an air duster. Next, 1 to 2 mL of ion-exchanged water is dropped on the surface of each sanitary ware, and the non-woven fabric portion of a sponge (Scotch-Brite (registered trademark) hybrid bonding sponge, manufactured by 3M Japan) is pressed against the surface with a load of 50 g / cm ² . From the state, the sponge was reciprocated 6000 times.

9.0 to 10.0 mg of silica (Si), 1.0 to 2.0 mg each of sodium (Na), calcium (Ca) and magnesium (Mg), and 0 potassium Commercially available water containing ~1.0 mg was diluted 5.5 times with deionized water to prepare test water. 200 μL of this test water was dropped on the sanitary ware surface after durability test 1, the sanitary ware surface after durability test 2, or the sanitary ware surface after durability test 3, and the temperature was set to 25° C. and the humidity to 70% under atmospheric pressure. Water scale was formed on the surface by drying for 16 hours in a constant temperature and humidity bath.

A bathroom sponge (Scotch Bright (registered trademark) Bath Shine antibacterial sponge (with special abrasive particles), manufactured by 3M Japan) is soaked with ion-exchanged water, and the surface of the sponge is coated with a bathroom detergent (Bath Magiclean Foaming Spray, manufactured by Kao). was pushed (about 1 mL sprayed) to prepare a foamed detergent. The surface of the sponge was pressed against the surface of the sanitary ware on which limescale was formed with a load of 200 g/cm ² and slid back and forth five times.

After sliding, it was visually confirmed whether the scale on the surface of the sanitary ware was completely removed. It was judged to be ○ when it was completely removed, and to be × when even a little scale remained. The results are shown in Table 7 below.

1 substrate for sanitary ware 2 glaze layer 3 perfluoropolyether chain 10 sanitary ware

Claims (6)

A sanitary ware comprising a substrate for sanitary ware and a glaze layer provided on the surface of the substrate,
The glaze layer has a surface arithmetic mean line roughness Ra of 0.03 μm or more and 2.5 μm or less,
The surface of the sanitary ware comprises perfluoropolyether chains,
All carbon atoms having C—F bonds and bonded thereto in the perfluoropolyether chain, obtained by peak separation of the spectrum obtained by X-ray photoelectron spectroscopy (XPS) measurement of the surface of the sanitary ware The ratio of the number of all fluorine atoms having a C-F bond to the total number of oxygen atoms is 1.1 or more and 1.7 or less,
The ratio of the number of carbon atoms having a _CF3 bond in the perfluoropolyether chain to the total number of carbon atoms having a CF bond in the perfluoropolyether chain obtained by the peak separation is 20 at% or less. Sanitary ware characterized by: 2. The sanitary ware according to claim 1, wherein said glaze layer has a surface arithmetic mean linear roughness Ra of 0.03 μm or more and 1.5 μm or less. The sanitary ware according to claim 2, wherein the glaze layer has a surface arithmetic mean linear roughness Ra of 0.03 µm or more and 1.0 µm or less. The ratio of the number of all fluorine atoms having a CF bond to the total number of all carbon atoms having a CF bond and oxygen atoms bonded thereto in the perfluoropolyether chain is 1.1 or more and 1.5 The sanitary ware according to any one of claims 1 to 3, wherein: In the profile obtained by XPS depth direction analysis, the XPS measurement point on the surface of the sanitary ware is set as _the starting point, and the peak area (A The sputtering time is 60 seconds or less until the end point where the ratio of the absolute value of the difference between a) and the fluorine atom peak area (A _b ) at the measurement point one point before is _1.0 at% or less. The sanitary ware according to any one of items 1 to 3. In the profile obtained by XPS depth direction analysis, the XPS measurement point on the surface of the sanitary ware is set as _the starting point, and the peak area (A The sputtering time is 60 seconds or less until the end point where the ratio of the absolute value of the difference between a) and the fluorine atom peak area (A _b ) at the measurement point one point before is _1.0 at% or less. Item 4. The sanitary ware according to item 4.

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