Member provided with a glass substrate

Abstract

Provided is a member having a glass substrate, which can continuously prevent the attachment of dirt even after long-term use while being repeatedly cleaned, and can continuously remove the attached dirt easily, that is, with a small cleaning load. A member having a glass substrate, wherein the glass substrate contains silicon (Si) atoms and oxygen (O) atoms as main component elements, and Ia metal atoms and / or IIa metal atoms as arbitrary component elements, a surface of the member contains a perfluoropolyether chain, and a ratio of a Sn atom concentration to a Si atom concentration (Sn atom concentration / Si atom concentration) of the surface of the member, which is calculated from peak areas of a Si2p spectrum and a Sn3d5 spectrum measured by X-ray photoelectron spectroscopy (XPS), is greater than 0.05.

Description

TECHNICAL FIELD

[0001] The present application relates to a member having a glass substrate. In detail, it relates to a glass member having both good stain resistance and high durability. BACKGROUND

[0002] Glass substrates are used for various purposes, for example, mirrors are used for washing the face, makeup, and the like. On such a wash basin mirror, a makeup mirror, various stains are easily attached depending on the use conditions. For example, makeup is usually used by the user in close proximity to the mirror, and thus makeup such as mascara is easily attached to the mirror. In order to remove the stains such as makeup attached to the mirror, dry wiping cleaning using a dry cloth or the like and / or water wiping cleaning using a cloth or the like containing water is usually performed. However, water wiping traces can remain on the surface of the mirror, become fixed in the form of water stains, and can impair the appearance of the mirror, and even impair the original function of the mirror.

[0003] A wash basin mirror is a mirror provided above the inner side of a wash basin for washing the face and hands, and is used when various actions using water are performed. For example, actions in which water droplets are easily scattered, such as washing the hands, rinsing the mouth, washing the face, and brushing the teeth, can be cited as examples of the method of use. Furthermore, these actions are performed every day as a matter of course in daily life. The manner of use is various, and water droplets can sometimes be heavily attached, in which case, even if a dry cloth or the like is used to wipe them off, wiping traces of the water droplets and stains can remain on the surface of the mirror, and water wiping traces as if water wiping cleaning had been performed can remain on the surface of the mirror. The wash basin is present in front, and thus it is difficult to wipe the mirror with a cloth while applying force when cleaning the wiping traces. Furthermore, if wiping traces remain, the appearance of the mirror can be impaired, and even the original function of the mirror can be impaired.

[0004] Furthermore, a wash basin mirror is a residential device, and thus the user does not usually frequently replace it, and it is expected that it will be used for ten years even if only for a short time. In particular, in the case of a device for use with water, the cleaning is performed as if it were a strong rubbing action because the stains are mostly heavy. Thus, it is required that even in use conditions in which such a load is applied, no scratches or stains are attached to the mirror even over a long period of time.

[0005] In public facilities, wash basin mirrors and makeup mirrors also exist in large numbers, and because many people frequently use them, water droplets are scattered in large quantities, and various makeup stains can also be attached. On the other hand, as wash basin mirrors and makeup mirrors, there are also many cases in which a large area is required. In this case, it is difficult to completely wipe off the stains attached to the mirror, and if the stains cannot be completely wiped off, many people can be bothered by the stains and wiping traces when they use the mirror. Thus, for example, there is a problem in that, in a hotel or a commercial facility or the like, it is difficult for a cleaner to clean the mirror completely, and it takes time.

[0006] Therefore, in order to prevent dirt from adhering to the surface of the glass substrate and also improve the removal of dirt, a technique of modifying the surface of the substrate by covering it with a protective layer or the like is used.

[0007] However, there is a problem that the surface of the substrate is colored by providing a protective layer on the glass substrate, or the appearance of the substrate is impaired due to damage / peeling of the protective layer or the like. In order to solve this problem, a monomolecular film that is chemically bonded to the glass substrate has been used. The monomolecular film is a thin layer that cannot be visually confirmed, and therefore by providing the monomolecular film, the function of the monomolecular film can be imparted without impairing the appearance of the substrate. Furthermore, the monomolecular film is chemically bonded to the glass substrate, and therefore the durability of the film is also improved.

[0008] For example, a monomolecular film containing a fluoroalkylsilane compound is known to protect the surface of a glass substrate, and has a dirt-proof effect. For example, in Japanese Patent Application Publication No. 2005-206447 (Patent Document 1), a glass member formed by forming a coating film on a glass sheet is disclosed, the coating film containing: a substance in which a carbon fluoride group, a hydrocarbon group, and a silyl group are main components, and a substance in which a siloxane group is a main component. It is considered that this glass member is a glass member in which the durability such as abrasion resistance and weather resistance, water droplet repellency (water slide property), and dirt resistance are improved in a glass sheet in which water / oil / dirt resistance is required (paragraph 0005). Furthermore, in Patent Document 1, it is described that when a float glass is used as the glass sheet, and a water / oil / dirt resistance coating film is formed in advance on a tin-containing surface, it is convenient in terms of improving durability (paragraph 0040).

[0009] On the other hand, in recent years, a technique of applying a compound containing a perfluoropolyether chain, which has superior adhesion to a glass substrate and durability to a fluoroalkylsilane compound, to the surface of the substrate has been proposed.

[0010] For example, in Japanese Patent Application Publication No. 2010-31184 (Patent Document 2), a surface treatment agent composition containing a perfluorooxyalkylene-containing polymer is proposed, and the object is to particularly improve the surface slide property when wiping off dirt from the surface of a touch panel. Furthermore, in Patent Document 2, a glass member in which a perfluorooxyalkylene-containing polymer contained in the composition is vacuum-deposited on the surface of a sliding glass is disclosed. The member has a low dynamic friction coefficient even after an abrasion test, has good surface slide property, and has excellent sebum dirt wiping-off property.

[0011] Further, in Japanese Patent Application Publication No. 2016-204656 (Patent Literature 3), a surface treatment agent containing a fluorine-containing polyether group-modified silane is proposed, which aims to particularly improve the abrasion resistance when wiping off dirt from the surface of a touch panel. Further, a glass member obtained by spraying the surface treatment agent on the surface of Gorilla (registered trademark) Glass 3 (manufactured by Corning Incorporated) is disclosed in Patent Literature 3. The member has a good contact angle with water (water repellency) after an abrasion test, and it is considered that the abrasion resistance is exerted.

[0012] Note that Gorilla (registered trademark) Glass is a glass mainly used for smartphones, in which the strength such as scratch resistance is improved by chemical strengthening.

[0013] Further, in Japanese Patent Application Publication No. 2012-157856 (Patent Literature 4), a glass member is disclosed, which is obtained by forming a cured condensed film of a silane containing a perfluoropolyether group on a material obtained by polishing, washing with water, and drying the surface of a float glass substrate. It is considered that the glass member has low dust adhesion, good dust removal properties, and good oil removal properties in the state where dust is adhered (paragraph 0057).

[0014] Prior Art Documents

[0015] Patent Literature

[0016] Patent Literature 1: Japanese Patent Application Publication No. 2005-206447

[0017] Patent Literature 2: Japanese Patent Application Publication No. 2010-31184

[0018] Patent Literature 3: Japanese Patent Application Publication No. 2016-204656

[0019] Patent Literature 4: Japanese Patent Application Publication No. 2012-157856 SUMMARY

[0020] PROBLEMS TO BE SOLVED BY THE INVENTION

[0021] The present inventors and others have confirmed that even in glass members that generally contain a perfluoropolyether chain considered to have high durability on the surface, there are members that lose function over time, that is, when used for a long time while being repeatedly cleaned. Also, recently, a new type of glass member that has both good stain resistance and higher durability, particularly, sliding resistance, has been found. That is, it has been found that by applying a perfluoropolyether chain to the surface of a glass substrate having an inherent surface composition, even after long-term use while being repeatedly cleaned (whereby a sliding force or an abrasion force is loaded to the surface of the member), it is possible to continuously prevent the attachment of stains such as cosmetics, scale, and the like, and it is possible to easily, that is, with a small cleaning load, continuously remove the attached stains. The present invention was completed based on these insights.

[0022] Solution to the problem

[0023] The member of the present invention is characterized by having a glass substrate containing silicon (Si) atoms and oxygen (O) atoms as main component elements, and Ia metal atoms and / or IIa metal atoms as arbitrary component elements, and a surface containing a perfluoropolyether chain, and a ratio of a Sn atom concentration to a Si atom concentration (Sn atom concentration / Si atom concentration) of the surface of the member calculated from the peak areas of a Si2p spectrum and a Sn3d5 spectrum measured by X-ray photoelectron spectroscopy (XPS) is greater than 0.05.

[0024] Effects of the invention

[0025] According to the present invention, even after long-term use while being repeatedly cleaned, it has excellent durability against a sliding force or an abrasion force loaded to the surface of the member by cleaning, and thus it is possible to continuously prevent the attachment of stains. Furthermore, it is possible to easily, that is, with a small cleaning load, continuously remove the attached stains. Therefore, a glass member that can maintain both stain resistance and easy removability for a long time is provided. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 (a) of FIG. 1 is a schematic view showing one example of a glass member of the related art, showing that a fluoroalkyl chain exists in a vertical direction on a glass substrate. Figure 1 (b) of FIG. 1 is a schematic view showing one example of a glass member of the present invention, showing that a perfluoropolyether chain exists in a horizontal direction inclined on a glass substrate.

[0027] Figure 2 is a graph showing O1s spectra obtained by performing XPS measurement on the glass members of Examples 1 to 9 and Comparative Examples 1 to 2.

[0028] Figure 3 is a graph showing F1s spectra obtained by performing XPS measurement on the glass members of Examples 1 to 9 and Comparative Examples 1 to 2.

[0029] Figure 4 is a graph showing the Cls spectrum obtained by subjecting the glass member of Example 1 to XPS measurement.

[0030] Figure 5 is a graph showing the Sn3d5 spectrum obtained by subjecting the glass member of Example 1 to XPS measurement.

[0031] Figure 6 is a graph showing the Si2p spectrum obtained by subjecting the glass member of Example 1 to XPS measurement.

[0032] Figure 7 is a graph showing the Nal s spectrum obtained by subjecting the glass member of Example 1 to XPS measurement.

[0033] Figure 8 is a graph showing the Ca2p spectrum obtained by subjecting the glass member of Example 1 to XPS measurement.

[0034] Figure 9 is a graph showing the result of peak separation of the Ols spectrum obtained by subjecting the glass member of Example 1 to measurement into three peaks (CF2-O-CF2, Si-O-H, Si-O-Si).

[0035] Figure 10 is a graph showing the result of peak separation of the Ols spectrum obtained by subjecting the glass member of Example 5 to measurement into three peaks (CF2-O-CF2, Si-O-H, Si-O-Si).

[0036] Figure 11 is a graph showing the result of peak separation of the Ols spectrum obtained by subjecting the glass member of Comparative Example 2 to measurement into three peaks (CF2-O-CF2, Si-O-H, Si-O-Si).

[0037] Figure 12 is a graph showing the spectrum obtained by subjecting the glass member of Example 5, and a glass member produced in the same manner as Example 5 except that no pretreatment was performed, to TOF-SIMS measurement.

[0038] Explanation of Reference Numerals:

[0039] 1: glass substrate; 2: fluoroalkyl chain; 3: perfluoropolyether chain. DETAILED DESCRIPTION

[0040] Member having a glass substrate

[0041] <Configuration of member>

[0042] Figure 1 (b) is a schematic diagram showing a cross-sectional structure of one example of a member having a glass substrate (hereinafter, sometimes also referred to as "glass member" or "member") of the present application. The member of the present application is formed of a glass substrate 1. The member of the present application contains a perfluoropolyether chain 3 on its surface. Note that the present application does not exclude a scheme in which any constituent element (for example, an intermediate layer having a desired function) is included between the glass substrate 1 and the member surface containing the perfluoropolyether chain 3, within a range in which the effects of the present application can be exerted.

[0043] <Surface composition of member>

[0044] With respect to the member of the present application, the ratio of the Sn atomic concentration to the Si atomic concentration (Sn atomic concentration / Si atomic concentration) (hereinafter, sometimes also referred to as R Sn / Si ) calculated from the peak areas of the Si2p spectrum and the Sn3d5 spectrum according to the "XPS measurement conditions" described below, which are measured by X-ray photoelectron spectroscopy (XPS) on the surface of the member, is greater than 0.05. The member of the present application contains a perfluoropolyether chain on the surface of the member, and thus the adhesion of the perfluoropolyether chain to the surface of the glass substrate is good, and furthermore, the durability of the member surface containing the perfluoropolyether chain is also good. As a result, the member of the present application can exert excellent durability against the sliding force or the abrasion force loaded on the member surface due to cleaning, and can maintain both the stain resistance and the easy removability of dirt for a long time, even after long-term use while being repeatedly cleaned. Moreover, in the present application, water marks are not easily left after water wiping cleaning, and thus water scale is not easily formed, and as a result, the adhesion of water scale can be prevented for a long time.

[0045] <Effect mechanism>

[0046] The reason why the member of the present application exerts the above-described effects can be considered to be the following mechanism, but is not limited thereto. In the surface of the member of the present application, a specific amount of Sn atoms is preferably uniformly dispersed in the surface direction, and thus the interaction between the perfluoropolyether chain and the surface of the glass substrate is uniformly exerted, and thus the interaction between the two can be made stronger, and a more stable state of the two can be formed. Therefore, it can be considered that the perfluoropolyether chain can be uniformly left on the surface of the member even after long-term use of the member while being repeatedly cleaned. As a result, it can be considered that the perfluoropolyether chain can be left in a state of firmly adhering to the surface of the glass substrate for a long time. According to such an effect mechanism, it can be considered that the member of the present application can maintain both the stain resistance against water mark left after water wiping cleaning and the easy removability of dirt such as cosmetics for a long time.

[0047] SnO2is easier to form a hydroxyl group than SiO2. Therefore, it can be considered that in the glass substrate containing Sn in a prescribed amount or more on the surface, a hydroxyl group is formed in a prescribed amount or more. Such a surface is easy to adsorb dirt because the surface energy becomes high. Therefore, in the related art, it is generally considered to remove Sn from the glass substrate, but in the present application, it is possible to consider utilizing the characteristic that SnO2easily forms a hydroxyl group, and to promote the bonding of the glass substrate to the perfluoropolyether chain.

[0048] Further, Sn atoms have a characteristic that the atomic diameter is large and the coordination number is large (typically, Si is 4-coordinated and Sn is 6-coordinated) compared to Si atoms. It can be considered that the interaction of Sn atoms with the perfluoropolyether chain is strong, and a stable state is formed.

[0049] On the other hand, the perfluoropolyether chain is a chain in which carbon atoms to which fluorine atoms are bonded and ether bonds in which the carbon atoms are bonded via oxygen atoms are included in a repeating structure, and for example, includes a repeating unit represented by -[(CF2) x -O]- (x is a natural number). Specifically, it is a chain in which one or more of each of the ether bonds as the (CF2)-O, (C2F4)-O, (C3F6)-O, (C4F8)-O, and the like are randomly bonded, and a plurality of O atoms are present in the chain. It can be considered that a hydrogen bond is formed between the oxygen atom in the perfluoropolyether chain and the above-described hydroxyl group derived from the glass substrate, and further, a coordination bond or the like is formed between the oxygen atom in the perfluoropolyether chain and the tin atom, and the stability between the glass substrate and the perfluoropolyether chain is improved.

[0050] <R Sn / Si of the Preferred Range

[0051] As for the amount of Sn on the surface of the member, it is preferable that the more, the better, as long as the member is not colored. In the present application, the lower limit value of R Sn / Si of the surface of the member is preferably 0.06 or more, and more preferably 0.07 or more. Further, from the viewpoint of coloring of the member, the upper limit value of R Sn / Si is preferably less than 0.5, and more preferably less than 0.4. The preferable range of R Sn / Si may combine these upper and lower limit values, and is more preferably greater than 0.05 and less than 0.5, and further preferably 0.06 or more and less than 0.4.

[0052] <Method for Calculating R Sn / Si of the Surface of the Member

[0053] In the present application, R Sn / SiThe surface of the member can be measured by X-ray photoelectron spectroscopy (XPS). That is, the respective concentrations of Sn atoms and Si atoms on the surface of the member are found by XPS. Note that the surface of the member is preferably cleaned of dirt before XPS measurement. For example, the surface of the member is preferably wiped clean with a cloth impregnated with ethanol, and degreasing is performed.

[0054] As the XPS device, for example, PHI Quantera II (manufactured by ULVAC-PHI) is used, and the surface of each member is measured using the following "XPS measurement conditions".

[0055] [XPS Measurement Conditions]

[0056] X-ray conditions (monochromatic Al Kα ray, 50 W, 15 kV).

[0057] Analysis area (200 μm φ).

[0058] Neutralization gun conditions (Emission: 20 μA).

[0059] Ion gun conditions (Emission: 7.0 mA).

[0060] Photoelectron take-off angle (45°).

[0061] Time per step (50 ms).

[0062] Sweep (five times).

[0063] Pass energy (55 eV).

[0064] Measured elements (scanning in the order of O, F, C, Sn, Si, Na, and Ca)

[0065] Scanning range (O1s: 523 to 543 eV, F1s: 679 to 699 eV, C1s: 278 to 308 eV, Sn3d5: 480 to 500 eV, Si2p: 94 to 114 eV, Na1s: 1066 to 1086 eV, and Ca2p: 341 to 361 eV).

[0066] The O 1s spectrum, the F 1s spectrum, the C 1s spectrum, the Sn 3d5 spectrum, the Si 2p spectrum, the Na 1s spectrum, and the Ca 2p spectrum derived from the surface of the member were obtained by XPS measurement. Based on the obtained spectra, the atomic concentrations were calculated using the data analysis software PHI MultiPak VERSION 9 (manufactured by ULVAC-PHI). After smoothing the obtained spectra and calibrating the Na 1s peak charge to 1072.1 eV, the peaks based on the electron orbitals of the respective atoms were background-subtracted by the Shirley method. Then, the peak area intensities were calculated, and the analysis was performed by dividing by the sensitivity coefficients inherent to the device, which were set in advance in the data analysis software, to calculate the atomic concentrations. Specifically, the oxygen atomic concentration (hereinafter referred to as C O ), the fluorine atomic concentration (hereinafter referred to as C F ), the carbon atomic concentration (hereinafter referred to as C C ), the tin atomic concentration (hereinafter referred to as C Sn ), the silicon atomic concentration (hereinafter referred to as C Si ), the sodium atomic concentration (hereinafter referred to as C Na ), and the calcium atomic concentration (hereinafter referred to as C Ca ) were calculated. In the calculation of the concentrations, the oxygen was calculated using the peak area of the O 1s peak (529 to 539 eV), the fluorine was calculated using the peak area of the F 1s peak (683 to 693 eV), the carbon was calculated using the peak area of the C 1s peak (283 to 299 eV), the tin was calculated using the peak area of the Sn 3d5 peak (482 to 492 eV), the silicon was calculated using the peak area of the Si 2p peak (98 to 108 eV), the sodium was calculated using the peak area of the Na 1s peak (1067 to 1077 eV), and the calcium was calculated using the peak area of the Ca 2p peak (345 to 355 eV). The values of the atomic concentrations can be set to the average values obtained by measuring four different places. In the case where an abnormal value is present in the four places, the average value is calculated by removing the abnormal value. Using the obtained tin atomic concentration C Sn and the silicon atomic concentration C Si , R Sn / Si was calculated according to the following formula (A).

[0067] R Sn / Si = C Sn / C Si ... Formula (A)

[0068] In the case where the perfluoropolyether chain forming layer is thick and the peaks derived from the glass substrate are not detected in the XPS measurement of the surface of the member, R' Sn / Si of the surface of the glass substrate can be calculated by removing or reducing the perfluoropolyether chain-containing layer contained in the surface of the member by heating or UV irradiation, as described later (about R' Sn / Si ).

[0069] glass substrate

[0070] In the present application, the glass substrate contains silicon (Si) atoms and oxygen (O) atoms as main component elements, and further contains Ia metal atoms and / or Ha metal atoms as optional component elements. The Ia metal atoms refer to lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr). The Ha metal atoms refer to beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra). Of these, it is preferable to contain one or more selected from the group consisting of sodium (Na), potassium (K), magnesium (Mg), and calcium (Ca) as optional component elements.

[0071] In the present application, the glass substrate further contains tin (Sn) atoms on its surface.

[0072] In the present application, with respect to the glass substrate, it is preferable that the ratio (Sn atom concentration / Si atom concentration) (hereinafter, sometimes referred to as R Sn ) of the tin (Sn) atom concentration (hereinafter, C Si ) on the surface thereof, which is calculated from the peak areas of the Si2p spectrum and the Sn3d5 spectrum according to the XPS measurement conditions described above, to the silicon (Si) atom concentration (hereinafter, C Sn / Si ) is greater than 0.05. With respect to the XPS measurement of the surface of the glass substrate, the same apparatus and conditions as those for the XPS measurement of the surface of the member described above can be used.

[0073] In the XPS measurement of the surface of the glass substrate, the Ols peak, the Si2p peak, the Sn3d5 peak, the Nals peak, and the Ca2p peak are detected. By performing the same process on the obtained Si2p spectrum and Sn3d5 spectrum as the process performed to obtain R Sn / Si of the surface of the member described above, R Sn / Si of the surface of the glass substrate can be obtained according to the following equation (B).

[0074] R Sn / Si = C Sn / C Si ... Equation (B)

[0075] With respect to the amount of Sn on the surface of the glass substrate, it is preferable that the more, the better, provided that the glass substrate is not colored. In the present application, the lower limit value of R Sn / Si of the surface of the glass substrate is preferably 0.06 or greater, and more preferably 0.07 or greater. Further, from the viewpoint of coloring of the glass substrate, R Sn / Si is preferably less than 0.5, and more preferably less than 0.4.

[0076] R Sn / SiR of the surface of the glass member Sn / Si There is a correlation. Therefore, by performing XPS measurement on the surface of the glass member, R of the surface of the glass substrate can be estimated. Sn / Si It is considered that the reason is that the perfluoropolyether chain is contained in the surface of the glass member at a density that does not affect the concentration of Sn atoms and Si atoms present on the surface of the glass substrate.

[0077] As the glass substrate, a material generally known as glass can be used. For example, a glass that is inorganic and has transparency, such as a float glass produced by a float method used in architectural glass, or a soda-lime glass produced by a roll out method, can be used. In the present application, it is preferable to adjust the amount of Sn of the surface of such a glass. Specifically, it is preferable to introduce tin to the surface of the glass in a manner to become a desired amount of Sn. As the method of introducing tin, a method of introducing at the time of glass production, a method of introducing after the glass production can be exemplified. As the method of introducing at the time of glass production, a method of introducing at the time of production by a float method can be exemplified. As the method of introducing after the glass production, for example, a method of implanting Sn atoms to the surface of the glass substrate by a PVD method such as vacuum evaporation, ion plating method, sputtering method, CVD method; a method of forming a layer containing Sn atoms on the surface of the glass substrate by spraying or the like can be exemplified.

[0078] As the shape of the glass substrate, a flat plate, a curved plate, or the like can be used, and the size and the thickness are not particularly limited. The surface of the glass substrate opposite to the surface (surface of the member) containing the perfluoropolyether chain (back surface of the member) can also be a reflective surface.

[0079] Perfluoropolyether chain

[0080] The perfluoropolyether chain 3 contained in the surface of the member is a chain containing a carbon atom to which a fluorine atom is bonded and an ether bond in which the carbon atom is bonded via an oxygen atom in a repeating structure, and contains, for example, a repeating unit represented by -[(CF2) x -O]- (x is a natural number). Specifically, it is a chain in which one or more of each ether bond as a repeating unit of (CF2)-O, (C2F4)-O, (C3F6)-O, (C4F8)-O, or the like is randomly bonded. In the present application, it is preferable that the total number of repeating units be large, and more preferably be 200 or less. Therefore, the perfluoropolyether chain 3 is characterized in that the chain of each molecule is relatively long. It is considered that the perfluoropolyether chain 3 has excellent flexibility and exhibits interaction with the substrate.

[0081] The reason why the perfluoropolyether chain 3 is flexible can be considered as follows, but the present application is not limited thereto. As described above, it can be considered that the perfluoropolyether chain 3 has a fluorine atom and an oxygen atom bonded to a carbon atom. Generally, an atom bonded to a carbon atom is located at a vertex of a tetrahedral structure, and thus can freely rotate around a carbon single bond. Therefore, an infinite number of stereoscopic conformations can be obtained. In the case of a chain containing an ether bond such as a perfluoropolyether chain, the interaction between two carbon atoms bonded to the oxygen atom of the ether bond becomes less likely to occur due to the presence of the oxygen atom therebetween, and there is almost no energy difference caused by the position of the twist. Therefore, an organic chain containing an ether bond can rotate more freely around a carbon-oxygen single bond. For example, compared with a fluoralkyl chain or the like not having an ether bond, the shape of a perfluoropolyether chain having a large number of ether bonds changes with a high degree of freedom. That is, it can be considered that the perfluoropolyether chain 3 having a large number of ether bonds, that is, a large number of repeating units, or in other words, a long chain length per molecule, is excellent in flexibility (softness).

[0082] According to the excellent flexibility of the perfluoropolyether chain 3, for example, a load such as a sliding force or an abrasion force applied to the surface of the member by wiping or the like can be dispersed or released. As a result, it can be considered that the surface of the member of the present application can have excellent durability.

[0083] In the present application, the longer the molecular chain of the perfluoropolyether chain 3, that is, the larger the number of repeating units, the more preferable it is within a range in which it can function well. Thereby, it can be considered that the flexibility of the perfluoropolyether chain 3 is further improved.

[0084] Further, the perfluoropolyether chain 3 has a long chain length per molecule and is flexible, and thus it is presumed that, as shown in (b) of Figure 1 , the perfluoropolyether chain 3 exists obliquely in a horizontal direction (a surface direction) with respect to the surface of the glass substrate 1. Thereby, the distance between the surface of the glass substrate and the perfluoropolyether chain becomes short, and thus it can be considered that an interaction is exerted between the perfluoropolyether chain and Sn atoms contained in the surface of the glass substrate. The atomic diameter of a Sn atom is large compared with that of a Si atom, and the coordination number is large (typically, Si is 4-coordinated, and Sn is 6-coordinated), and thus it can be considered that the interaction of the Sn atom with the perfluoropolyether chain is strong, and a stable state is formed. Through the above-described interaction, it can be considered that the adhesion of the perfluoropolyether chain to the surface of the glass substrate is improved, and as a result, the durability of the member is also improved.

[0085] On the other hand, the fluoralkyl chain 2 used conventionally is generally short in molecular chain and is rigid, and thus, as shown in (a) of Figure 1 , it can be considered that it exists in a vertical direction with respect to the surface of the glass substrate. Therefore, the distance between the surface of the glass substrate and the fluoralkyl chain 2 is long, and it can be considered that even in the case where Sn atoms are contained in the surface of the glass substrate, the interaction exerted between the fluoralkyl chain 2 and the Sn atoms is weak.

[0086] The perfluoropolyether chain 3 is preferably linear. It is considered that, because it is linear, the steric hindrance is less than that of a branched structure, and the probability of interaction with Sn in the base material increases. Therefore, it is considered that the adhesion to the base material increases.

[0087] According to the excellent flexibility of the perfluoropolyether chain 3 described above, and the strong interaction with Sn atoms contained in the surface of the base material 1, the member of the present application has excellent durability against the sliding force or the abrasion force loaded on the surface of the member due to cleaning, even after long-term use while being repeatedly cleaned, and thus can maintain its functions, both the antifouling property and the easy removability of dirt, for a long time.

[0088] In the present application, as the perfluoropolyether chain 3, the perfluoropolyether chain 3 represented by the following Formula 1 is generally preferred.

[0089]

[0090] In Formula 1, a, b, c, and d are the number of repeating units, that is, an integer of 0 or more, the sum of a, b, c, and d is 3 to 200, and the chain can be a chain in which each repeating unit in the formula is randomly bonded, or a chain in which each polymer chain composed of each repeating unit is bonded to each other. In addition, with respect to the repeating unit, it can contain only a linear chain, or can contain a branched chain. R1and R2each represent an organic chain containing one or more selected from a carbon atom, an oxygen atom, a nitrogen atom, a hydrogen atom, and a fluorine atom. For example, an alkyl chain (— (CH2) n — ); a fluoroalkyl chain (— (CF2) n — ); an organic chain containing both of these; a chain containing an ether bond in one or more selected from an alkyl chain, a fluoroalkyl chain, and an organic chain containing both of these can be exemplified. In addition, either one of R1or R2may be a terminal, or both of R1and R2may have a terminal group bonded thereto. Here, the number of repeating units of the perfluoropolyether chain of Formula 1 is the number calculated by liquid analysis of a raw material containing the perfluoropolyether chain of Formula 1 using 19 F-NMR. In addition, as needed, it is sometimes sought to additionally perform 1 H-NMR, 13 C-NMR, DEPT135, MALDI-MS analysis. It is considered that the structure (number of repeating units) of the perfluoropolyether chain contained in the raw material and the member produced using the raw material is not changed in the manufacturing process of the member, and thus the number of repeating units of the perfluoropolyether chain contained in the member can be calculated by liquid analysis of the raw material. In the case where the raw material has been diluted with a solvent and is difficult to analyze, liquid analysis is performed after being concentrated to a certain concentration or more.

[0091] In the present application, it is preferable that the perfluoropolyether chain 3 is formed by polymerization of 10 to 200 perfluoroether groups. In formula 1, a + b + c + d is preferably 10 to 200, more preferably 10 to 150, and most preferably 20 to 100. By this, durability can be further improved.

[0092] As the perfluoropolyether chain 3, further preferable are, for example, perfluoropolyether chains represented by the following formulas 2 to 8.

[0093]

[0094] In formula 2, e:f:g = 23.2:22.3:0.4 (average), and the repeating units in the formula are arranged randomly. e + f + g = 45.9.

[0095] Here, the number of repeating units of the perfluoropolyether chain of formula 2 is the number calculated by liquid analysis using F-NMR on a raw material containing the perfluoropolyether chain of formula 2. It is considered that the structure (number of repeating units) of the perfluoropolyether chain contained in the raw material and in a member produced using the raw material is not changed in the production process of the member, and thus the number of repeating units of the perfluoropolyether chain contained in the member can be calculated by liquid analysis of the raw material. 19 F-NMR. It is considered that the structure (number of repeating units) of the perfluoroether chain contained in the raw material and in a member produced using the raw material is not changed in the production process of the member, and thus the number of repeating units of the perfluoroether chain contained in the member can be calculated by liquid analysis of the raw material.

[0096]

[0097] In formula 3, h:i:j = 22.3:20.2:0.5 (average), and the repeating units in the formula are arranged randomly. h + i + j = 43.0. Here, the number of repeating units of the perfluoropolyether chain of formula 3 is the number calculated by liquid analysis using F-NMR on a raw material containing the perfluoropolyether chain of formula 3. It is considered that the structure (number of repeating units) of the perfluoropolyether chain contained in the raw material and in a member produced using the raw material is not changed in the production process of the member, and thus the number of repeating units of the perfluoropolyether chain contained in the member can be calculated by liquid analysis of the raw material. 19 F-NMR. It is considered that the structure (number of repeating units) of the perfluoroether chain contained in the raw material and in a member produced using the raw material is not changed in the production process of the member, and thus the number of repeating units of the perfluoroether chain contained in the member can be calculated by liquid analysis of the raw material.

[0098]

[0099] (Formula 4, average of k is 22.9). Here, the number of repeating units of the perfluoropolyether chain of formula 4 is the number calculated by liquid analysis using F-NMR on a raw material containing the perfluoropolyether chain of formula 4. It is considered that the structure (number of repeating units) of the perfluoropolyether chain contained in the raw material and in a member produced using the raw material is not changed in the production process of the member, and thus the number of repeating units of the perfluoropolyether chain contained in the member can be calculated by liquid analysis of the raw material. 19 F-NMR. It is considered that the structure (number of repeating units) of the perfluoroether chain contained in the raw material and in a member produced using the raw material is not changed in the production process of the member, and thus the number of repeating units of the perfluoroether chain contained in the member can be calculated by liquid analysis of the raw material.

[0100]

[0101] (In formula 5, the average value of 1 is 23.4). Here, the number of repeating units of the perfluoropolyether chain of formula 5 is a number calculated by liquid analysis of a raw material containing the perfluoropolyether chain of formula 5 using19F-NMR. It is considered that the structure (number of repeating units) of the perfluoropolyether chain contained in the raw material and a member made using the raw material is not changed in the manufacturing process of the member, and thus the number of repeating units of the perfluoropolyether chain contained in the member can be calculated by liquid analysis of the raw material. 19 F-NMR. It is considered that the structure (number of repeating units) of the perfluoropolyether chain contained in the raw material and a member made using the raw material is not changed in the manufacturing process of the member, and thus the number of repeating units of the perfluoropolyether chain contained in the member can be calculated by liquid analysis of the raw material.

[0102]

[0103] (In formula 6, the average value of m is 23.2). Here, the number of repeating units of the perfluoropolyether chain of formula 6 is a number calculated by liquid analysis of a raw material containing the perfluoropolyether chain of formula 6 using19F-NMR. It is considered that the structure (number of repeating units) of the perfluoropolyether chain contained in the raw material and a member made using the raw material is not changed in the manufacturing process of the member, and thus the number of repeating units of the perfluoropolyether chain contained in the member can be calculated by liquid analysis of the raw material. 19 F-NMR. It is considered that the structure (number of repeating units) of the perfluoropolyether chain contained in the raw material and a member made using the raw material is not changed in the manufacturing process of the member, and thus the number of repeating units of the perfluoropolyether chain contained in the member can be calculated by liquid analysis of the raw material.

[0104]

[0105] (In formula 7, the average value of n is 18). Here, the number of repeating units of the perfluoropolyether chain of formula 7 is a number calculated by liquid analysis of a raw material containing the perfluoropolyether chain of formula 7 using19F-NMR. It is considered that the structure (number of repeating units) of the perfluoropolyether chain contained in the raw material and a member made using the raw material is not changed in the manufacturing process of the member, and thus the number of repeating units of the perfluoropolyether chain contained in the member can be calculated by liquid analysis of the raw material. 19 F-NMR. It is considered that the structure (number of repeating units) of the perfluoropolyether chain contained in the raw material and a member made using the raw material is not changed in the manufacturing process of the member, and thus the number of repeating units of the perfluoropolyether chain contained in the member can be calculated by liquid analysis of the raw material.

[0106]

[0107] (In formula 8, the average value of p is 24). Here, the number of repeating units of the perfluoropolyether chain of formula 8 is a number calculated by liquid analysis of a raw material containing the perfluoropolyether chain of formula 8 using19F-NMR. It is considered that the structure (number of repeating units) of the perfluoropolyether chain contained in the raw material and a member made using the raw material is not changed in the manufacturing process of the member, and thus the number of repeating units of the perfluoropolyether chain contained in the member can be calculated by liquid analysis of the raw material. 19 F-NMR. It is considered that the structure (number of repeating units) of the perfluoropolyether chain contained in the raw material and a member made using the raw material is not changed in the manufacturing process of the member, and thus the number of repeating units of the perfluoropolyether chain contained in the member can be calculated by liquid analysis of the raw material.

[0108] The surface of the member containing a perfluoropolyether chain can be determined, for example, by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS). The evaluation method is described below.

[0109] First, the surface of the member is evaluated by X-ray photoelectron spectroscopy (XPS) to obtain spectra of C 1s, F 1s, and O 1s. In the spectra, a peak of fluorine atoms having a C-F bond (peak position: 687 eV to 690 eV) in F 1s is obtained, and a peak of carbon atoms having a C-F bond (peak position: 290 eV to 297 eV) in C 1s is obtained, whereby it is known that the surface of the member contains a C-F bond. As examples of compounds containing a C-F bond, compounds containing a perfluoroether bond, fluoroalkyl compounds, and the like can be considered. Further, a peak of oxygen atoms having a CF2-O-CF2 bond (peak position: 535 eV to 538 eV) in O 1s is obtained, whereby it is possible to confirm that the surface of the member contains a perfluoroether bond. Note that the XPS measurement is performed using the above-described device and "XPS measurement conditions".

[0110] The method of confirming the peak of oxygen atoms having a CF2-O-CF2 bond (peak position: 535 eV to 538 eV) in O 1s is as follows. The O 1s spectrum obtained by XPS measurement is separated into three peaks. The peak tops of the three peaks are set to CF2-O-CF2 (536 eV), Si-O-H (533 eV), and Si-O-Si (532 eV), respectively, and spectral peak fitting processing is performed using a Gauss-Lorentz (Gauss-Lorentz) function with a Shirley method. From each peak after the processing, a CF2-O-CF2 peak area (hereinafter referred to as A CF2－O－CF2 ), a Si-O-H peak area (hereinafter referred to as A Si－O－H ), and a Si-O-Si peak area (hereinafter referred to as A Si－O－Si ) are calculated. It is considered that CF2-O-CF2 is a peak derived from a perfluoroether, and Si-O-H and Si-O-Si are peaks derived from a glass substrate. In the case where the value of A CF2－O－CF2 is 20 or more, it is said that a perfluoroether is present. When it is preferably present at 30 or more, and more preferably at 35 or more, the effect can be more favorably obtained.

[0111] Further, the evaluation method of the surface of the member by TOF-SIMS is as follows. As the TOF-SIMS device, for example, TOF.SIMS 5 (ION-TOF Corporation) can be used. TOF-SIMS is an analysis method of detecting secondary ions generated from the surface of a sample when pulsed primary ions irradiated from a primary ion source are irradiated to the surface of the sample. The kind of the generated secondary ions, the detection sensitivity differ depending on the composition, the chemical structure of the surface of the sample. By visualizing the distribution of various secondary ions of the surface of the sample, the distribution of the composition, the chemical structure of the surface of the sample can be estimated.

[0112] By using the following measurement conditions, the surface measurement of the member by TOF-SIMS can obtain the secondary ion mass spectrum of the compound in the form of the horizontal axis: mass number (m / z, that is, the value of mass m divided by charge z), the vertical axis: secondary ion intensity (count).

[0113] [TOF-SIMS measurement conditions]

[0114] Primary ion source: Bi.

[0115] Ion irradiation amount: 5E9 ions / cm 2 .

[0116] Measurement area: 200 μm square.

[0117] Mass range: 0 to 800.

[0118] Sputtering ion source: Ar-GCIB.

[0119] Measurement cycle: 120.

[0120] Detected ion: positive.

[0121] Sputtering rate: 0.3 nm / cycle (acrylate conversion).

[0122] In the secondary ion mass spectrum obtained using the above measurement conditions, it can be confirmed that the surface of the member contains a perfluoropolyether chain from the periodically appearing fragments. In the case where fragments periodically appearing with an equal mass interval exist in the high mass side of the secondary ion mass spectrum m / z of several hundreds or more, the molecular formula of the repeating unit contained in the compound can be inferred from the mass interval. The same can be inferred for the case where a plurality of repeating units exist. From the existence of the CF2-O-CF2 bond obtained by XPS, and the degree of agreement of the precise mass with the isotope obtained by TOF-SIMS, it can be known that the molecular formula of the repeating unit is C x F y O zIn the case where (x, y, z are integers of 1 or more, and y = 2x), a perfluoroether is contained as a repeating unit. Further, the total number of repeating units is at least several or more, as indicated by the fragments that occur at equal intervals and periodically. By the above TOF-SIMS analysis, it is indicated that when the repeating unit contains a perfluoroether and the total number of repeating units is at least three or more, the surface of the member contains a perfluoropolyether chain 3.

[0123] In the present application, the compound containing the perfluoropolyether chain 3 is preferably bonded to a Si atom. The perfluoropolyether chain 3 is bonded to the Si atom via an organic group or directly, whereby the durability of the surface of the member is improved. Further, it is preferable that the compound containing the perfluoropolyether chain 3 is bonded to the surface of the glass substrate 1 via a Si atom. Thereby, the adhesion of the perfluoropolyether chain 3 to the surface of the glass substrate 1 is improved. Further, in the present application, it is more preferable that the Si atom bonded to the compound containing the perfluoropolyether chain 3 is bonded to an O atom, and the Si atom is bonded to the surface of the glass substrate 1 via the O atom. Thereby, the adhesion of the perfluoropolyether chain 3 to the surface of the glass substrate 1 is further improved.

[0124] The compound containing the perfluoropolyether chain 3 is preferably bonded to the surface of the glass substrate 1 via a Si atom and an O atom. The bonding state can be determined, for example, by surface-enhanced Raman spectroscopy (SERS), Si-NMR, and infrared spectroscopy (IR), and the like. 19 Si-NMR, and infrared spectroscopy (IR), and the like.

[0125] The compound containing the perfluoropolyether chain 3 is preferably bonded to the glass substrate 1 via a plurality of Si atoms. Thereby, the adhesion of the perfluoropolyether chain 3 to the surface of the glass substrate 1 is improved. The Si atom is preferably bonded to a side chain of the compound containing the perfluoropolyether chain 3, and the Si atom is more preferably bonded to a terminal of the compound containing the perfluoropolyether chain 3. The Si atom can be bonded to both terminals of the compound containing the perfluoropolyether chain 3, and the Si atom can be bonded to a single terminal of the compound containing the perfluoropolyether chain 3. The Si atom bonded to the compound containing the perfluoropolyether chain 3 can be derived from a reactive silane group contained in a raw material that is bonded to the compound containing the perfluoropolyether chain 3, or can be a Si atom generated by the activation of the surface of the glass substrate.

[0126] Further, in the present application, it is preferable that a C atom of the compound containing the perfluoropolyether chain 3 is bonded to a Sn atom of the surface of the glass substrate 1 via a Si-O chain. That is, the surface of the glass substrate 1 forms a Sn-O-Si-C bond with the compound containing the perfluoropolyether chain 3, whereby the surface of the member of the present application can obtain particularly excellent durability.

[0127] The member is evaluated by TOF-SIMS, whereby it is possible to confirm that the member contains Sn-O-Si-C bonds. In the case where the perfluoropolyether chain-containing compound 3 is bonded to Si atoms, it is considered that the perfluoropolyether chain-containing compound 3 is bonded to the glass substrate 1 via Si atoms.

[0128] A method for confirming that the member contains Sn-O-Si-C bonds is described below. First, the surface of the member is measured by TOF-SIMS in accordance with the following condition 2, and the obtained spectrum is normalized in accordance with the following condition 3.

[0129] (Condition 2)

[0130] Measurement device: ION-TOF Corporation TOF.SIMS 5.

[0131] Primary ion source: Bi.

[0132] Ion irradiation amount: 5E9 ions / cm2 2 .

[0133] Measurement area: 200 μm square.

[0134] Mass range: 0 to 800.

[0135] Sputtering ion source: Ar-GCIB.

[0136] Measurement period: 120.

[0137] Detection ion: Positive.

[0138] Sputtering rate: 0.3 nm / period (acrylic acid conversion).

[0139] (Condition 3)

[0140] The average value of Sn in the 110 to 120 periods of the spectrum measured in accordance with condition 2 is calculated, normalized, and multiplied by each coefficient (the following formula C) for each fragment. The coefficients are SiOH: 3000, F: 2000, SiCH3O: 2000, and Sn: 2000.

[0141] (Peak count value x coefficient) / (average value of Sn count in 110 to 120 periods)... (Formula C)

[0142] In the normalized spectrum, the peak position of the peak F (m / z = 19) derived from the perfluoropolyether chain is defined as the value of one cycle of the value of one-half of the value of one cycle at the interface of the glass substrate and the perfluoropolyether chain. At this interface, by confirming the decrease of both the peak SiCH30 (m / z = 59) derived from the terminal group of the perfluoropolyether chain-containing compound and the peak Sn (m / z = 120) derived from the glass substrate, it is considered that the silanol group at the terminal of the perfluoropolyether chain-containing compound bonds to the Sn contained in the surface of the glass substrate to generate a Sn-O-Si-C bond. That is, it is considered that the member contains the Sn-O-Si-C bond.

[0143] In the present application, a plurality of perfluoropolyether chains 3 exist at a high density on the surface of the member, and thus a film or layer containing the perfluoropolyether chain 3 can also be formed. The film containing the perfluoropolyether chain 3 is preferably a thin film. In the case where the film or layer containing the perfluoropolyether chain 3 is formed, the thickness thereof is preferably 1 nm or more and 10 nm or less, and more preferably 1 nm or more and 5 nm or less.

[0144] Method for manufacturing member

[0145] Preparation process of glass substrate

[0146] First, a glass substrate is prepared. The glass substrate is prepared so that the ratio of the tin (Sn) atomic concentration to the silicon (Si) atomic concentration (Sn atomic concentration / Si atomic concentration, R Sn / Si ) calculated from the peak areas of the Si2p spectrum and the Sn3d5 spectrum by X-ray photoelectron spectroscopy (XPS) in accordance with the above XPS measurement conditions is greater than 0.05. In this preparation process, by performing XPS measurement on the surface of the glass substrate, it is confirmed that the R Sn / Si value is greater than 0.05. As a result, if the above necessary condition is satisfied, the next step of pretreatment is performed. In the case where the necessary condition is not satisfied, the surface of the glass substrate is treated to increase the Sn atoms on the surface of the glass substrate. As the treatment method, a method of implanting Sn atoms into the surface of the glass substrate by a PVD method such as vacuum evaporation, ion plating, sputtering, or a CVD method; a method of forming a layer containing Sn atoms on the surface of the glass substrate by spraying or the like can be used. Then, XPS measurement is performed again on the surface of the glass substrate, and it is confirmed that the R Sn / Si value is greater than 0.05.

[0147] Pretreatment process

[0148] Next, the prepared glass substrate is subjected to pretreatment. In the present application, the pretreatment of the surface of the glass substrate means that the Sn atomic concentration of the surface of the glass substrate is not excessively decreased, and that the R Sn / Sia treatment for removing dirt present on the surface of the glass substrate within a range of not more than 0.05 and activating the hydroxyl group of the surface. This pretreatment process includes a process for removing dirt present on the surface of the glass substrate and / or a process for activating the hydroxyl group of the surface of the glass substrate. The R' of the surface of the glass substrate is preferably within a range of 0.05 or less, and more preferably within a range of 0.01 or less. Sn / Si This is performed within the above range. As a method of pretreatment, in a wet method, a method in which ultrasonic cleaning is performed while the glass substrate is immersed in an aqueous solution containing an alkaline detergent, or a method in which the glass substrate is wiped with a nonwoven fabric waste or the like impregnated with the aqueous alkaline detergent solution can be given. Further, a method in which an aqueous solution to which a neutral detergent is added, an aqueous solution to which an acidic detergent is added, a glass polishing agent, or a hydrofluoric acid-based agent is used instead of the aqueous solution to which the alkaline detergent is added can also be given. In a dry method, a method in which the surface of the glass substrate is subjected to UV irradiation or plasma irradiation is given. As the wavelength at the time of UV irradiation, λ = 308 nm, 254 nm, 222 nm, 185 nm, 172 nm, 146 nm, or 126 nm can be used. As the plasma irradiation, atmospheric pressure plasma or medium vacuum plasma can be used.

[0149] As described above, by performing pretreatment on the surface of the glass substrate, the hydroxyl group of the surface of the glass substrate can be activated, and the pretreatment can also maintain the state in which Sn atoms are uniformly dispersed in the surface direction on the surface of the glass substrate.

[0150] <Formation of perfluoropolyether chain>

[0151] Next, a perfluoropolyether chain is formed on the surface of the glass substrate after the pretreatment. The formation of the perfluoropolyether chain can be performed by applying a treatment liquid containing a compound containing a perfluoropolyether chain to the surface of the glass substrate. The method of applying the treatment liquid containing the compound containing a perfluoropolyether chain can use a publicly known method. For example, the application can be performed by coating using immersion treatment, spin coating, bar coating, wiping, vacuum evaporation, a spray gun, or the like. After the treatment liquid containing the compound containing a perfluoropolyether chain is coated on the surface of the glass substrate, drying is performed, and, if necessary, curing is performed, and then, as the case requires, wiping of the surface of the member with a dry cloth or a cloth containing water, or cleaning using a neutral detergent and a sponge is preferably performed, and then, after sufficient rinsing with water, a glass member in which a perfluoropolyether chain is contained on the surface of the member can be obtained.

[0152] As the treatment liquid containing a compound containing a perfluoropolyether chain, any treatment liquid can be used as long as a member of the present application can be produced. As the compound containing a perfluoropolyether chain, for example, a compound containing a chain in which one or more - [(CF2) xa chain in which each ether bond of a repeating unit represented by -0-(x is a natural number), specifically, (CF2)-0, (C2F4)-0, (C3F6)-0, (C4F8)-0, or the like is randomly bonded. As a specific example of the compound containing a perfluoropolyether chain, a compound containing a structure represented by the following Chemical Formula 9 can be given.

[0153]

[0154] Here, a, b, c, d are the number of repeating units, that is, an integer of 0 or more, and the sum of a, b, c, d is 3 to 200. It can be a chain in which each repeating unit is randomly bonded, or a chain in which each polymer chain composed of each repeating unit is bonded to each other. In addition, each repeating unit can include a straight chain or a branched chain. R1and R2each represent an organic chain containing one or more selected from a carbon atom, an oxygen atom, a nitrogen atom, a hydrogen atom, and a fluorine atom. For example, an alkyl chain (— (CH2) n — ); a fluoroalkyl chain (— (CF2) n — ); an organic chain containing both of them; and a chain containing an ether bond in one or more selected from an alkyl chain, a fluoroalkyl chain, and an organic chain containing both of them. In addition, either one of R1or R2may be a terminal, or a terminal group can be bonded to both of R1and R2. The number of repeating units of the perfluoropolyether chain is determined by liquid analysis using 19 F-NMR. In addition, as needed, it is sometimes determined by additionally performing 1 H-NMR, 13 C-NMR, DEPT135, and MALDI-MS analysis. In a case where the liquid has been diluted with a solvent to such an extent that it is difficult to analyze, liquid analysis is performed after being concentrated to a certain concentration or more.

[0155] Further, as a specific compound containing a perfluoropolyether chain, a compound containing a structure represented by the following Chemical Formulas 10 to 12 can be given.

[0156]

[0157] In Formula 10, e:f:g = 23.2:22.3:0.4 (average), and the repeating units in the formula are randomly arranged. e+f+g = 45.9. The number of repeating units of the perfluoropolyether chain is determined by liquid analysis using 19 F-NMR.

[0158]

[0159] In formula 11, h:i:j = 22.3:20.2:0.5 (average), and the repeating units in the formula are arranged randomly. h+i+j = 43.0. The number of repeating units of the perfluoropolyether chain is determined by 19 F-NMR was performed for liquid analysis.

[0160]

[0161] In formula 12, the average value of k is 22.9. The number of repeating units of the perfluoropolyether chain is determined by 19 F-NMR was performed for liquid analysis.

[0162]

[0163] In formula 13, the average value of 1 is 23.4. The number of repeating units of the perfluoropolyether chain is determined by 19 F-NMR was performed for liquid analysis.

[0164]

[0165] In formula 14, the average value of m is 23.2. The number of repeating units of the perfluoropolyether chain is determined by 19 F-NMR was performed for liquid analysis.

[0166]

[0167] In formula 15, the average value of n is 18. The number of repeating units of the perfluoropolyether chain is determined by 19 F-NMR was performed for liquid analysis.

[0168]

[0169] In formula 16, the average value of p is 24. The number of repeating units of the perfluoropolyether chain is determined by 19 F-NMR was performed for liquid analysis.

[0170] The perfluoropolyether chain-containing compound is preferably a compound containing a perfluoropolyether chain and at least one Si atom. The perfluoropolyether chain is preferably bonded to the Si atom via an organic group or directly. The effect of the perfluoropolyether chain bonded to the Si atom via an organic group or directly is as described above. The perfluoropolyether chain-containing compound is further preferably a compound in which the perfluoropolyether chain is bonded to at least one reactive silane group.

[0171] The reactive silyl group is preferably a functional group having an organic group not containing a fluorine atom, and a hydroxyl group or a hydrolysable group bonded to a Si atom. The hydrolysable group is specifically an alkoxy group, a halogenated group, or the like, and more specifically -OCH3, -OCH2CH3, -Cl, or the like. The hydroxyl group or the hydrolysable group contained in the reactive silyl group preferably functions as a bonding point to the surface of the glass substrate. That is, the hydroxyl group contained in the reactive silyl group, or the hydrolysable group hydrolyzes to give a hydroxyl group, or the hydrogen atom contained in the hydroxyl group dehydrates and condenses with a functional group (a hydrogen atom or a hydroxyl group, or the like) present on the surface of the glass substrate. Thus, the perfluoropolyether chain-containing compound can be bonded to the surface of the glass substrate. In the present application, the reactive silyl group preferably contains a plurality of bonding points to the surface of the glass substrate, that is, hydroxyl groups or hydrolysable groups. Thus, the adhesion of the perfluoropolyether chain-containing compound to the surface of the glass substrate is improved.

[0172] In the present application, the treatment liquid containing the perfluoropolyether chain-containing compound can also be diluted with a suitable solvent. As such a solvent, for example, fluorinated aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, or the like), fluorinated aromatic hydrocarbon solvents (hexafluoro-m-xylene, trifluorotoluene, or the like), fluorinated ether solvents (methyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), ethyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, or the like), fluorinated alkyl amine solvents (perfluorotributylamine, perfluorotripentylamine, or the like), hydrocarbon solvents (petroleum ether, mineral spirits, toluene, xylene, or the like), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, or the like) can be exemplified. Among them, from the viewpoints of solubility, wettability, and the like, fluorinated solvents are preferred, and hexafluoro-m-xylene, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, and mixtures thereof are particularly preferred.

[0173] Use

[0174] The member of the present application can be used in the use for the usual glass products within the range satisfying the above constitution and characteristics. For example, it can be used as a mirror, a window glass, a glass-made door, a wall or a shelf, or a smart mirror, or the like.

[0175] According to a preferred aspect of the present application, the member of the present application can be a glass member used in a water-use place, for example, a glass member used in a washstand, a restroom, a bathroom, a shower booth. Further, the member of the present application can be a touch panel, a glass-made display panel used in a water-use place. As specific examples of these, a washstand mirror, a dressing mirror, a bathroom mirror, a bathroom door, a bathroom window glass, a bathroom shelf, a shower booth wall, a shower booth door, a shower booth shelf can be exemplified. Further, a smart mirror used in a water-use place space such as a washstand, a restroom, a bathroom, a shower booth, or the like can be exemplified.

[0176] In using these members, in order to improve the antifogging property or the like of the surface, a heating member (for example, a heater) can be provided in the vicinity of the member.

[0177] [Examples]

[0178] The present application is further explained by the following examples. It should be understood that the present application is not limited to these examples.

[0179] 1. Preparation

[0180] 1-1. Glass substrate

[0181] Glass substrates A to E were prepared by immersing a float glass in a 3% aqueous potassium hydroxide solution at 80°C for a prescribed time (0 to 60 minutes).

[0182] The surface of each of the prepared glass substrates was measured by XPS to confirm the atomic concentration of the surface of each of the glass substrates. Before the measurement, in order to remove dirt from the surface of each of the glass substrates, the surface of the glass substrate was wiped clean with a nonwoven cloth tip (Bemcot, Asahi Kasei) impregnated with ethanol, thereby performing degreasing.

[0183] As the XPS device, a PHI Quantera II (manufactured by ULVAC-PHI) was used, and the surface of each of the glass substrates was measured in accordance with the following "XPS measurement conditions".

[0184] [XPS Measurement Conditions]

[0185] X-ray conditions (monochromatic Al Kα ray, 50 W, 15 kV).

[0186] Analysis area (200 μm φ).

[0187] Neutralization gun conditions (emission: 20 μA).

[0188] Ion gun conditions (emission: 7.0 mA).

[0189] Photoelectron take-off angle (45°).

[0190] Time per step (50 ms).

[0191] Scanning (five times).

[0192] Energy (55 eV).

[0193] Measured elements (scanning in the order of O, Sn, Si, Na, and Ca).

[0194] Scanning range (O 1s: 523 to 543 eV, Sn 3d 5: 480 to 500 eV, Si 2p: 94 to 114 eV, Na 1s: 1066 to 1086 eV, Ca 2p: 341 to 361 eV).

[0195] By XPS measurement, O 1s spectrum, Sn 3d 5 spectrum, Si 2p spectrum, Na 1s spectrum, Ca 2p spectrum were obtained. Based on the obtained spectra, atomic concentrations were calculated using data analysis software PHI MultiPak VERSION 9 (manufactured by ULVAC-PHI). After smoothing treatment was performed on the obtained spectra, and Na 1s peak charge was calibrated to 1072.1 eV, peaks based on electron orbits of each atom were background-removed by Shirely method. Then, each peak area intensity was calculated, and analysis processing was performed by dividing by sensitivity coefficients inherent to the device which were previously set in the data analysis software, and each atomic concentration was calculated. Specifically, oxygen atomic concentration (hereinafter referred to as C O ), tin atomic concentration (hereinafter referred to as C Sn ), silicon atomic concentration (hereinafter referred to as C Si ), sodium atomic concentration (hereinafter referred to as C Na ), and calcium atomic concentration (hereinafter referred to as C Ca ) were calculated. In the calculation of the concentrations, oxygen was the peak area of O 1s peak (529 to 539 eV), tin was the peak area of Sn 3d 5 peak (482 to 492 eV), silicon was the peak area of Si 2p peak (98 to 108 eV), sodium was the peak area of Na 1s peak (1067 to 1077 eV), and calcium was the peak area of Ca 2p peak (345 to 355 eV). The value of each atomic concentration can be set to the average value of four different measurements. Among them, in the case where an abnormal value appears in the four, the average value is calculated by removing the abnormal value. The obtained C O , C Si , C Sn , C Ca , and C Na (atomic concentration %) are shown in Table 1.

[0196] Using C Sn and C Si obtained by XPS, R Sn / Si was calculated according to the following formula (B).

[0197] R Sn / Si = C Sn / C Si ... Formula (B)

[0198] The obtained R Sn / Si is shown in Table 1.

[0199] [Table 1]

[0200]

[0201] 1-2. Reagents

[0202] The following Reagents a to c containing a compound containing a perfluoropolyether chain or a compound containing a fluoroalkyl chain were prepared. In the structural formula of the effective ingredient contained in each reagent, X Si means a group containing at least one Si atom, and the Si atom is bonded to an organic group not containing a fluorine atom and a hydroxyl group or a hydrolyzable group. The hydrolyzable group means an alkoxy group, a halogenated group. Specifically, it is -OCH3, -OCH2CH3, -Cl.

[0203] Reagent a

[0204] Reagent containing a compound containing a perfluoropolyether chain represented by formula (a) as an effective ingredient, which is composed of the following ingredients.

[0205]

[0206] (Formula a, l:m:n = 22.3:20.2:0.5 (average), X Si means a group containing an average of 1.0 Si atom, and the Si atom is bonded to an organic group not containing a fluorine atom and a hydroxyl group or a hydrolyzable group. The hydrolyzable group means an alkoxy group, a halogenated group. Specifically, it is -OCH3, -OCH2CH3, -Cl. Note that the repeating units in the formula are randomly arranged. These values are obtained by liquid analysis of Reagent a using NMR. The number average molecular weight of the perfluoropolyether chain was confirmed from the results of F-NMR, and in addition, the presence of X 19 was confirmed from the detection spectrum of H-NMR and Si-NMR.) Si 1 29

[0207] (Ingredients)

[0208] • Hexafluoro-m-xylene (CAS No. 402-31-3): 80-90%.

[0209] • Silicone compound containing a perfluoropolyether chain represented by formula (a) (effective ingredient): 10-20%.

[0210] Reagent b

[0211] Reagent containing a compound containing a perfluoropolyether chain represented by formula (b) as an effective ingredient, which is composed of the following ingredients.

[0212]

[0213] ​​​(In formula b, the average values of 1 : m : n = 23.2 : 22.3 : 0.4, X Si comprises an average of 3.0 Si atoms, and otherwise is the same as X Si of formula (a). These values were determined by liquid analysis of reagent b using NMR. The number average molecular weight of the perfluoropolyether chain was determined from 19 F-NMR results, and the presence of X Si was confirmed from the detection spectrum of H-NMR and 1 Si-NMR. 29

[0214] (Components)

[0215] • Fluoroalkyl ether (CAS No. 163702-06-5): 40-50%.

[0216] • Fluoroalkyl ether (CAS No. 163702-05-4): 30-40%.

[0217] • Compound containing perfluoropolyether chain of formula (b) (active ingredient): 10-20%.

[0218] Reagent c

[0219] Reagent containing, as an active ingredient, a compound containing a perfluoropolyether chain of formula (c), composed of the following components.

[0220]

[0221] (In formula c, the average value of n is 22.9. X Si comprises an average of 2.0 Si atoms, and otherwise is the same as X Si of formula (a). These values were determined by liquid analysis of reagent c using NMR. The number average molecular weight of the perfluoropolyether chain was determined from 19 F-NMR results, and the presence of X Si was confirmed from the detection spectrum of H-NMR and 1 Si-NMR. 29

[0222] (Components)

[0223] • Ethyl nonafluorobutyl ether (CAS No. 163702-05-4): 25-35%.

[0224] • Ethyl nonafluoroisobutyl ether (CAS No. 163702-06-5): 45-55%.

[0225] • Compound containing perfluoropolyether chain of formula (c) (active ingredient): 15-25%. ​​

[0226] reagent d

[0227] A reagent consisting of the following components, with a compound containing a perfluoropolyether chain as shown in formula (d) as the active ingredient.

[0228]

[0229] (In formula d, the average value of n is 23.4, which was determined by liquid analysis of reagent d using NMR. The number-average molecular weight of the perfluoropolyether chain is based on...) 19 The results of F-NMR confirmed this. Furthermore, X... Si It contains an average of 3.0 Si atoms, and in addition, X is consistent with that in equation (a). Si same.)

[0230] (Element)

[0231] • Ethyl nonafluorobutyl ether (CAS No. 163702-05-4): 25-35%.

[0232] • Ethyl nonafluoroisobutyl ether (CAS No. 163702-06-5): 45-55%.

[0233] • Compounds containing a perfluoropolyether chain of formula (d) (active ingredient): 15-25%.

[0234] reagent e

[0235] A reagent consisting of the following components, with a compound containing a perfluoropolyether chain as shown in formula (e) as the active ingredient.

[0236]

[0237] (In equation e, the average value of n is 23.2. X) Si It contains an average of 3.7 Si atoms, and in addition, X is similar to that in equation (a). Si Similarly, these values ​​were determined using NMR spectroscopy to analyze reagent e in liquid form. The number-average molecular weight of the perfluoropolyether chain is based on... 19 The results of F-NMR confirmed this, and X-rays also showed that... Si The existence of 1 H-NMR and 29 (Confirmed by Si-NMR detection spectra.)

[0238] (Element)

[0239] • Ethyl nonafluorobutyl ether (CAS No. 163702-05-4): 25-35%.

[0240] • Ethyl nonafluoroisobutyl ether (CAS No. 163702-06-5): 45-55%.

[0241] • Compound containing perfluoropolyether chain of formula (e) (active ingredient): 15-25%.

[0242] Reagent f

[0243] Reagent containing, as active ingredient, a compound containing a perfluoropolyether chain of formula (f).

[0244]

[0245] (In formula f, the average value of n is 18, which is determined by liquid analysis of reagent f using NMR. The number average molecular weight of the perfluoropolyether chain is determined from the average value of n and the molecular weight of the monomer of formula (f) according to the results of F-NMR. In addition, X 19 is the same as X Si in formula (a), except that it contains an average of 1.0 Si atom.) Si

[0246] (Ingredients)

[0247] • 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane (CAS No. 80793-17-5): 99.5% or more.

[0248] • Silane compound containing perfluoropolyether chain of formula (f) (active ingredient): less than 0.5%.

[0249] Reagent g

[0250] Reagent containing, as active ingredient, a compound containing a fluoroalkyl chain of formula (g).

[0251]

[0252] (In formula g, X Si contains an average of 1.0 Si atom, and is otherwise the same as X Si in formula (a).)

[0253] (Ingredients)

[0254] • Compound containing fluoroalkyl chain of formula (g) (active ingredient, CAS No. 83048-65-1) > 98.0%.

[0255] 1-3. Preparation of treatment liquid

[0256] To 30 g of fluorine solvent (product name: NOVEC 7200, 3M) was added dropwise 206 μL of reagent a, and gentle stirring was performed, to obtain treatment liquid a having an active ingredient concentration of reagent a of about 0.1 wt%.

[0257] ​By the same method, a treatment liquid b containing reagent b, a treatment liquid c containing reagent c, a treatment liquid d containing reagent d, and a treatment liquid e containing reagent e were obtained. Reagent f was used as the treatment liquid f as it was, without dilution with a fluorine solvent, because the effective component concentration of reagent f was 0.1 wt%.

[0258] To 30 g of a fluorine solvent (product name: NOVEC 7200, 3M), 0.03 g of reagent g was added, and gentle stirring was performed, to obtain a treatment liquid g having an effective component concentration of reagent g of about 0.1 wt%.

[0259] 2. Formation of perfluoropolyether chain

[0260] 2-1. Pretreatment of glass substrate

[0261] The glass substrates A to E were introduced into a light surface treatment device (PL-21-200 (S), Senengineering) at a position of about 2 mm from a light source, and UV ozone treatment was performed on the surface of each glass substrate for 5 minutes.

[0262] 2-2. Application of treatment liquid

[0263] The treatment liquids shown in Table 2 were applied to the surface of each glass substrate after pretreatment using an airbrush at a pressure of 0.04 MPa, and left to stand for 30 seconds. Then, drying was performed by heating in a drying oven at 120°C for 30 minutes, to obtain 11 samples.

[0264] 2-3. Post-washing

[0265] Each of the obtained samples was subjected to surface polishing with a sponge while pouring water, to remove excess treatment liquid, to obtain the members of Examples 1 to 9 and Comparative Examples 1 to 2.

[0266] 3. Analysis / evaluation method

[0267] The following analysis / evaluation was performed on each of the obtained members.

[0268] 3-1. Measurement of atomic concentration by XPS

[0269] The atomic concentration of the surface of each member was measured by XPS. Before measurement, in order to remove dirt from the surface of each member, the surface of each member was wiped with a nonwoven fabric yarn (Bemcot, Asahi Kasei) impregnated with ethanol, to perform degreasing.

[0270] As the XPS device, PHI Quantera II (ULVAC-PHI) was used, and the surface of each member was measured according to the following "XPS measurement conditions".

[0271] [XPS measurement conditions]

[0272] X-ray conditions (monochromatic Al Kα ray, 50 W, 15 kV).

[0273] Analysis area (200 μm φ).

[0274] Neutralization gun conditions (emission: 20 μA).

[0275] Ion gun conditions (emission: 7.0 mA).

[0276] Photoelectron take-off angle (45°).

[0277] Time per step (50 ms).

[0278] Scanning (five times).

[0279] Passing energy (55 eV).

[0280] Element to be measured (scanning in the order of O, F, C, Sn, Si, Na, Ca).

[0281] Scanning range (01s: 523 to 543 eV, F1s: 679 to 699 eV, C1s: 278 to 308 eV, Sn 3d5: 480 to 500 eV, Si 2p: 94 to 114 eV, Na 1s: 1066 to 1086 eV, Ca 2p: 341 to 361 eV).

[0282] By XPS measurement, O1s spectrum, F1s spectrum, C1s spectrum, Sn 3d5 spectrum, Si 2p spectrum, Na 1s spectrum, Ca 2p spectrum were obtained. Figures 2 to 8 From the obtained spectra, atomic concentrations were calculated using data analysis software PHI MultiPak VERSION 9 (manufactured by ULVAC-PHI). After smoothing the obtained spectra and calibrating the Na 1s peak charge to 1072.1 eV, the peaks based on the electron orbitals of the respective atoms were background-removed by the Shirley method. Then, the peak area intensities were calculated, and analysis processing was performed by dividing by the sensitivity coefficients inherent to the device, which were set in advance in the data analysis software, to calculate the atomic concentrations. Specifically, the oxygen atomic concentration (hereinafter referred to as C O ), the fluorine atomic concentration (hereinafter referred to as C F ), the carbon atomic concentration (hereinafter referred to as C C ), the tin atomic concentration (hereinafter referred to as C Sn ), the silicon atomic concentration (hereinafter referred to as C Si ), the sodium atomic concentration (hereinafter referred to as C Na ), and the calcium atomic concentration (hereinafter referred to as C Ca). In the calculation of the concentration, the peak area of the O Is peak (529 to 539 eV) for oxygen, the peak area of the F Is peak (683 to 693 eV) for fluorine, the peak area of the C Is peak (283 to 299 eV) for carbon, the peak area of the Sn 3d5peak (482 to 492 eV) for tin, the peak area of the Si 2p peak (98 to 108 eV) for silicon, the peak area of the Na Is peak (1067 to 1077 eV) for sodium, and the peak area of the Ca 2p peak (345 to 355 eV) for calcium. The value of each atomic concentration can be set to the average value of the four measurements. In the case where an abnormal value appears in the four measurements, the average value is calculated by removing the abnormal value. The obtained respective concentrations (atomic concentration %) of carbon atoms, fluorine atoms, oxygen atoms, silicon atoms, tin atoms, calcium atoms, and sodium atoms are shown in Table 2.

[0283] [Table 2]

[0284]

[0285] 3-2. R Sn / Si The calculation

[0286] Using the tin atom concentration C Sn and the silicon atom concentration C Si , R Sn / Si is calculated according to the following formula (A).

[0287] R Sn / Si = C Sn / C Si ... Formula (A)

[0288] The obtained value of R Sn / Si is shown in Table 3.

[0289] 3-3. Confirmation of fluorine ether

[0290] The O Is spectrum of Example 1 obtained in the above 3-1. is shown as Figure 9 , the O Is spectrum of Example 5 is shown as Figure 10 , and the O Is spectrum of Comparative Example 2 is shown as Figure 11 "Measured value". Each spectrum is separated into three peaks. The peak tops of the three peaks are set to CF2-O-CF2(536 eV), Si-O-H (533 eV), and Si-O-Si (532 eV), respectively, and the peak fitting process is performed using a Gaussian-Lorentz function with a Shirley method (described in Figures 9 to 11 "Peak fitting process" described in the specification). From each peak after the process, the CF2-O-CF2peak area (hereinafter referred to as A CF2－O－CF2 ), the Si-O-H peak area (hereinafter referred to as A Si－O－H ), and the Si-O-Si peak area (hereinafter referred to as ASi－O－Si ). The obtained A CF2－O－CF2 , A Si－O－H , A Si－O－Si values are shown in Table 3. Here, it can be considered that CF2-O-CF2 is a peak derived from the perfluoroether, Si-O-H and Si-O-Si are peaks derived from the glass substrate. In Figure 9 , 10 , the peak derived from the perfluoroether was confirmed, on the other hand, in Figure 11 , the peak derived from the perfluoroether was not confirmed. Therefore, in the case where the value of A CF2－O－CF2 is 20 or more, it can be said that the perfluoroether exists.

[0291] 3-4. Confirmation of Sn-O-Si-C bond

[0292] The surface of the member of Example 5 was measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS) in accordance with the following Condition 2, and the obtained spectrum was normalized in accordance with the following Condition 3. On the other hand, without performing the pretreatment of the glass substrate, except for this, the surface of the member produced by the same method as Example 5 was measured by TOF-SIMS in accordance with the following Condition 2, and the spectrum normalized in accordance with the following Condition 3 was obtained. Figure 12 shows the normalized TOF-SIMS spectrum of the member of Example 5 (produced by performing the pretreatment of the glass substrate), and the member produced by the same method as Example 5 except that the pretreatment of the glass substrate was not performed.

[0293] (Condition 2)

[0294] Measuring device: ION-TOF Co. TOF.SIMS 5.

[0295] Primary ion source: Bi.

[0296] Ion irradiation amount: 5E9 ions / cm 2 .

[0297] Measuring area: 200 μm square.

[0298] Mass range: 0 to 800.

[0299] Sputtering ion source: Ar-GCIB.

[0300] Measuring period: 120.

[0301] Detected ion: Positive.

[0302] Sputtering rate: 0.3 nm / period (acryl conversion).

[0303] (Condition 3)

[0304] The average value of Sn in the 110 to 120 cycles of the spectrum measured according to Condition 2 was calculated, normalized, and multiplied by each coefficient (Formula C below) for each fragment. The coefficients were SiOH: 3000, F: 2000, SiCH3O: 2000, and Sn: 2000.

[0305] (peak count value x coefficient) / (average value of Sn count in 110 to 120 cycles)... (Formula C)

[0306] The two obtained spectra were compared. As a result, the peak intensities of SiCH3O (m / z = 59) and Sn (m / z = 120) decreased. SiCH3O (m / z = 59) can be considered to be a peak derived from the terminal group of the compound containing the perfluoropolyether chain represented by Formula (b) contained in the treatment liquid b, and Sn (m / z = 120) can be considered to be a peak derived from the glass substrate. Since both peaks decreased, it can be considered that they reacted, i.e., it can be considered that the silanol group at the terminal of the compound containing the perfluoropolyether chain represented by Formula (b) contained in the treatment liquid bonded to Sn contained in the surface of the glass substrate, and a Sn-O-Si-C bond was formed. In Figure 12 In the TOF-SIMS spectrum shown in Formula (b), the value of the peak F (m / z) = 19 derived from the perfluoropolyether chain, which is one cycle value, was half the value at the 25th cycle. The values of SiCH3O and Sn at the 25th cycle are shown in Table 4.

[0307] 3-5. Erasability of mascara stains

[0308] A black dot in the shape of a 2 mm diameter circle was directly drawn on the surface of each member using a cosmetic mascara (media Rich Mascara S BK Glossy Black, Kanebo Cosmetics), and left to stand for 5 minutes. Then, three erasing operations (200 gf / cm 2 ) were performed manually using a microfiber cloth (ZMF-05, SYSTEM POLYMER). Then, the presence or absence of stains and erasing traces was confirmed visually. As a result, the case where stains and erasing traces could not be confirmed was evaluated as "O", and the case where stains and erasing traces could be confirmed was evaluated as "X". The results are shown in Table 3.

[0309] 3-6. Water erasing trace removability

[0310] A microfiber cloth (ZMF-05, SYSTEM POLYMER) was assembled in a clamp with a side length of 2 cm in such a manner that two pieces were overlapped, and 100 μL of ultrapure water was contained therein. A load (88 gf / cm 2), and the cloth impregnated with ultrapure water was pressed against the surface of each member. Then, the surface of each member was visually observed to confirm the presence or absence of water streaks. The case where the streaks could not be confirmed was evaluated as "0", and the case where the streaks could be confirmed was evaluated as "X". The results are shown in Table 3.

[0311] 3-7. Abrasion resistance test

[0312] A dry cloth (original checkered tablecloth, Kaunet) was used to slide back and forth 5200 times while applying a load (88 gf / cm 2 ) to the surface of each member. After the sliding, the surface of each member was washed with running water, and the water was removed with an air duster. The "eyelash dirt removability" and "water streak removability" of each member after the sliding were evaluated as described above. The results are shown in Table 3.

[0313] [Table 3]

[0314]

[0315] [Table 4]

[0316]

Claims

1. A component having a glass substrate, wherein, The glass substrate comprises: silicon atoms (Si atoms) and oxygen atoms (O atoms) as the main constituent elements, and Group I metal atoms and / or Group II metal atoms as arbitrary constituent elements. The surface of the component contains perfluoropolyether chains. The ratio of Sn atom concentration to Si atom concentration on the surface of the component, calculated based on the peak areas of the Si 2p and Sn 3d5 spectra measured by X-ray photoelectron spectroscopy (XPS), i.e., Sn atom concentration / Si atom concentration, is greater than 0.

05. The component contains Sn-O-Si-C bonds.

2. The component having a glass substrate according to claim 1, wherein, The perfluoropolyether chain is bonded to Si atoms, which are bonded to the surface of the glass substrate via O atoms.

3. The component having a glass substrate according to claim 1 or 2, wherein, The perfluoropolyether chain is formed by the polymerization of 10 to 200 perfluoroethers.

4. The component having a glass substrate according to claim 1 or 2, wherein, The component is a glass product used in washbasins, washrooms, bathrooms, or shower rooms.

5. The component having a glass substrate according to claim 3, wherein, The component is a glass product used in washbasins, washrooms, bathrooms, or shower rooms.

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