Antifouling substrate

Abstract

To provide an article having a surface-treated layer with high friction durability and chemical resistance.SOLUTION: An article has a base material, an intermediate layer above the base material, and a surface-treated layer lying directly above the intermediate layer and formed from a surface treatment agent containing a fluorine-containing silane compound contain. The intermediate layer contains Si-containing complex oxide.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to fluoropolyether group-containing compounds. [Background technology]

[0002] It is known that certain fluorine-containing silane compounds, when used for surface treatment of substrates, can provide excellent water repellency, oil repellency, antifouling properties, etc. Layers obtained from surface treatment agents containing fluorine-containing silane compounds (hereinafter also referred to as "surface treatment layers") are applied as so-called functional thin films to a wide variety of substrates, such as glass, plastics, textiles, sanitary products, and building materials (Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-218639 [Patent Document 2] Japanese Patent Application Laid-Open No. 2017-082194 Summary of the Invention [Problem to be solved by the invention]

[0004] The fluorine-containing silane compounds described in Patent Document 1 or Patent Document 2 can provide a surface treatment layer with excellent functions, but there is a demand for a surface treatment layer with higher friction durability and chemical resistance.

[0005] An object of the present disclosure is to provide an article having a surface treatment layer with higher friction resistance and chemical resistance. [Means for solving the problem]

[0006] The present disclosure includes the following aspects. [1] A substrate; an intermediate layer positioned on the substrate; a surface treatment layer formed from a surface treatment agent containing a fluorine-containing silane compound and positioned directly on the intermediate layer; and The intermediate layer comprises a composite oxide containing Si. [2] The article according to [1] above, wherein the composite oxide is a composite oxide of Si and another metal, and the other metal is one or more atoms selected from the transition metals of Groups 3 to 11 and the main metal elements of Groups 12 to 15 of the periodic table. [3] The article according to [1] or [2] above, wherein the composite oxide is a composite oxide of Si and another metal, and the other metal is one or more atoms selected from Ta, Nb, Zr, Mo, W, Cr, Hf, Al, Ti, and V. [4] The article according to any one of the above [1] to [3], wherein the molar ratio of Si to the other metal in the composite oxide is 10:90 to 99.9:0.1. [5] The article according to any one of the above [1] to [4], wherein the molar ratio of Si to the other metal in the composite oxide is 13:87 to 93:7. [6] The article according to any one of the above [1] to [5], wherein the molar ratio of Si to the other metal in the composite oxide is 45:55 to 75:25. [7] The article according to any one of the above [1] to [6], wherein the composite oxide is a composite oxide of Si and Ta or a composite oxide of Si and Nb. [8] The fluorine-containing silane compound is represented by the following formula (1) or (2): [ka] [In formula: R F1 independently in each occurrence, Rf 1 -R F -O q - and; R F2 is -Rf 2 p -R F -O q - and; Rf 1each occurrence independently represents C optionally substituted by one or more fluorine atoms; 1-16 is an alkyl group; Rf 2 C optionally substituted with one or more fluorine atoms 1-6 is an alkylene group; R F is independently in each occurrence a divalent fluoropolyether group; p is 0 or 1; q is independently in each occurrence 0 or 1; R Si is independently in each occurrence a monovalent group containing a silicon atom to which is bonded a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group; At least one R Si is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded; X A are each independently a single bond or a divalent to decavalent organic group; α is an integer from 1 to 9; β is an integer from 1 to 9; Each γ is independently an integer of 1 to 9. The article according to any one of the above [1] to [7], wherein the compound is at least one fluoropolyether group-containing compound represented by the following formula: [9] Rf 1 independently in each occurrence, C 1-16 is a perfluoroalkyl group, Rf 2 independently in each occurrence, C 1-6 is a perfluoroalkylene group, The item described in [8] above.

[10] R F may independently in each occurrence represent the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3RFa 6) d -(OC2F4) e -(OCF2) f - [In the formula, R Fa is independently in each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom; a, b, c, d, e, and f each independently represent an integer of 0 to 200, the sum of a, b, c, d, e, and f is 1 or more, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula. The article according to the above [8] or [9], wherein the group is represented by the formula:

[11] R Fa is a fluorine atom.

[12] R F is independently in each occurrence a formula (f1), (f2) or (f3): -(OC3F6) d - (f1) [In the formula, d is an integer of 1 to 200.] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2) [In the formula, c and d each independently represent an integer of 0 to 30; e and f are each independently an integer of 1 to 200; The sum of c, d, e, and f is an integer from 10 to 200; The order of occurrence of each repeating unit enclosed in parentheses with the subscript c, d, e, or f is arbitrary in the formula.] -(R 6 -R 7 ) g - (f3) [In the formula, R 6 is OCF2 or OC2F4; R 7 are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12or a combination of two or three groups selected from these groups; and g is an integer from 2 to 100. The article according to any one of the above [8] to

[11] , wherein the group is represented by the formula:

[13] R Si is expressed by the following formula (S1), (S2), (S3), or (S4): [ka] [In formula: R 11 is independently in each occurrence a hydroxyl group or a hydrolyzable group; R 12 is independently in each occurrence a hydrogen atom or a monovalent organic group; n1 is (SiR 11 n1 R 12 3-n1 ) units are each independently an integer of 0 to 3; X 11 is, independently in each occurrence, a single bond or a divalent organic group; R 13 is independently in each occurrence a hydrogen atom or a monovalent organic group; t is independently in each occurrence an integer from 2 to 10; R 14 is independently in each occurrence a hydrogen atom or a halogen atom; R a1 independently in each occurrence -Z 1 -SiR 21 p1 R 22 q1 R 23 r1 and; Z 1 is independently in each occurrence an oxygen atom or a divalent organic group; R 21 independently in each occurrence -Z 1’ -SiR 21’p1’ R 22’ q1’ R 23’ r1’ and; R 22 is independently in each occurrence a hydroxyl group or a hydrolyzable group; R 23 is independently in each occurrence a hydrogen atom or a monovalent organic group; p1, in each occurrence, is independently an integer from 0 to 3; q1, in each occurrence, is independently an integer from 0 to 3; r1, in each occurrence, is independently an integer from 0 to 3; Z 1’ is independently in each occurrence an oxygen atom or a divalent organic group; R 21’ independently in each occurrence -Z 1” -SiR 22” q1” R 23” r1” and; R 22’ is independently in each occurrence a hydroxyl group or a hydrolyzable group; R 23’ is independently in each occurrence a hydrogen atom or a monovalent organic group; p1' in each occurrence is independently an integer from 0 to 3; q1' is independently in each occurrence an integer from 0 to 3; r1' in each occurrence is independently an integer from 0 to 3; Z 1” is independently in each occurrence an oxygen atom or a divalent organic group; R 22” is independently in each occurrence a hydroxyl group or a hydrolyzable group; R 23” is independently in each occurrence a hydrogen atom or a monovalent organic group; q1″ in each occurrence is independently an integer from 0 to 3; r1″ is independently in each occurrence an integer from 0 to 3; R b1 is independently in each occurrence a hydroxyl group or a hydrolyzable group; R c1 is independently in each occurrence a hydrogen atom or a monovalent organic group; k1, in each occurrence, is independently an integer from 0 to 3; l1, in each occurrence, is independently an integer from 0 to 3; m1 in each occurrence is independently an integer from 0 to 3; R d1 independently in each occurrence -Z 2 -CR 31 p2 R 32 q2 R 33 r2 and; Z 2 is independently in each occurrence a single bond, an oxygen atom, or a divalent organic group; R 31 independently in each occurrence -Z 2’ -CR 32’ q2’ R 33’ r2’ and; R 32 independently in each occurrence -Z 3 -SiR 34 n2 R 35 3-n2 and; R 33 is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; p2, in each occurrence, is independently an integer from 0 to 3; q2 in each occurrence is independently an integer from 0 to 3; r2, in each occurrence, is independently an integer from 0 to 3; Z 2’is independently in each occurrence a single bond, an oxygen atom, or a divalent organic group; R 32’ independently in each occurrence -Z 3 -SiR 34 n2 R 35 3-n2 and; R 33’ is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; q2' is independently in each occurrence an integer from 0 to 3; r2' is independently in each occurrence an integer from 0 to 3; Z 3 is independently in each occurrence a single bond, an oxygen atom, or a divalent organic group; R 34 is independently in each occurrence a hydroxyl group or a hydrolyzable group; R 35 is independently in each occurrence a hydrogen atom or a monovalent organic group; n2 in each occurrence is independently an integer from 0 to 3; R e1 independently in each occurrence -Z 3 -SiR 34 n2 R 35 3-n2 and; R f1 is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; k2, in each occurrence, is independently an integer from 0 to 3; l2, in each occurrence, is independently an integer from 0 to 3; m2 in each occurrence is independently an integer from 0 to 3. The article according to any one of the above [8] to

[12] , wherein the group is represented by the formula:

[14] The article according to any one of [8] to

[13] above, wherein α, β, and γ are 1.

[15] X Aare each independently a trivalent organic group, α is 1 and β is 2 or α is 2 and β is 1, γ is 2, An article according to any one of [8] to

[14] above.

[16] The article according to any one of the above [1] to

[15] , wherein the substrate is a glass substrate.

[17] A method for producing an article having a substrate and a surface treatment layer formed thereon from a surface treatment agent containing a fluorine-containing silane compound, comprising: forming an intermediate layer containing a composite oxide containing Si by simultaneously depositing Si and another metal on the substrate; and forming a surface treatment layer directly on the intermediate layer; A method comprising:

[18] A surface treatment agent used in the production of the article according to any one of the above [1] to

[16] . [Effects of the Invention]

[0007] According to the present disclosure, an article having a surface treatment layer with better abrasion resistance and chemical resistance can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0008] The article of the present disclosure comprises a substrate; an intermediate layer positioned on the substrate; a surface treatment layer formed from a surface treatment agent containing a fluorine-containing silane compound and positioned directly on the intermediate layer; and The intermediate layer includes a composite oxide containing Si.

[0009] Substrates that can be used in the present disclosure may be made of any suitable material, such as glass, resin (which may be a natural or synthetic resin, for example, a common plastic material), metal, ceramics, semiconductors (silicon, germanium, etc.), fibers (woven fabrics, nonwoven fabrics, etc.), fur, leather, wood, ceramics, stone, etc., building materials, etc., sanitary products, etc.

[0010] For example, if the article to be manufactured is an optical component, the material constituting the surface of the substrate may be a material for optical components, such as glass or transparent plastic. Furthermore, if the article to be manufactured is an optical component, some layer (or film), such as a hard coat layer or an antireflection layer, may be formed on the surface (outermost layer) of the substrate. The antireflection layer may be either a single-layer or a multilayer. Examples of inorganic materials that can be used for the antireflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, Ta3O5, Nb2O5, HfO2, Si3N4, CeO2, MgO, Y2O3, SnO2, MgF2, and WO3. These inorganic materials may be used alone or in combination (e.g., as a mixture) of two or more of them. When a multilayer antireflection layer is used, it is preferable to use SiO2 and / or SiO for the outermost layer. When the product to be manufactured is an optical glass component for a touch panel, a transparent electrode, such as a thin film made of indium tin oxide (ITO) or indium zinc oxide, may be provided on a portion of the surface of the substrate (glass). Furthermore, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, a liquid crystal display module, etc., depending on the specific specifications.

[0011] The shape of the substrate is not particularly limited and may be, for example, a plate, a film, or other form. The surface region of the substrate on which the surface treatment layer is to be formed may be at least a part of the substrate surface, and may be appropriately determined depending on the application and specific specifications of the product to be manufactured.

[0012] In one embodiment, the substrate may be made of a material whose surface originally contains hydroxyl groups. Examples of such materials include glass, metals (especially base metals), ceramics, and semiconductors, which form natural or thermal oxide films on their surfaces. Alternatively, for materials such as resins, which do not have sufficient hydroxyl groups or do not originally contain hydroxyl groups, pretreatment can be performed to introduce or increase the number of hydroxyl groups on the substrate surface. Examples of such pretreatments include plasma treatment (e.g., corona discharge) and ion beam irradiation. Plasma treatment can introduce or increase hydroxyl groups on the substrate surface, and can also be used to clean the substrate surface (remove foreign matter, etc.). Another example of such pretreatment is a method in which an interfacial adsorbent having carbon-carbon unsaturated bond groups is first formed in the form of a monomolecular film on the substrate surface by the Langmuir-Blodgett method (LB method) or chemical adsorption, followed by cleavage of the unsaturated bonds in an atmosphere containing oxygen, nitrogen, or the like.

[0013] In another embodiment, the substrate may have at least a surface portion made of a material containing another reactive group, such as a silicone compound having one or more Si—H groups, or an alkoxysilane.

[0014] In a preferred embodiment, the substrate is glass, such as sapphire glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, or quartz glass, with chemically strengthened soda-lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glass being particularly preferred.

[0015] The intermediate layer is located on the substrate.

[0016] The intermediate layer may be formed so as to be in contact with the substrate, or may be formed on the substrate via another layer. In a preferred embodiment, the intermediate layer is formed so as to be in contact with the substrate.

[0017] The intermediate layer contains a composite oxide containing Si, that is, a composite oxide of Si and another metal.

[0018] Here, the composite oxide includes oxides in which oxides of multiple elements including Si form a homogeneous phase, so-called solid solutions, as well as oxides in which oxides of multiple elements form a heterogeneous phase and oxides of multiple elements are mixed. For example, composite oxides include SiO x (x=1~2) and M y O z (y=1 to 2, z=1 to 5), the intermediate layer may contain other metals with different oxidation states. The concentration of the other metal may vary along the thickness direction of the intermediate layer, for example, the intermediate layer may have a concentration gradient along the thickness direction of the intermediate layer, or the concentration may vary stepwise. Preferably, the composite oxide is composed of a solid solution that forms a homogeneous phase.

[0019] In this specification, the term "metal" also includes metalloids such as B, Si, Ge, Sb, As, and Te.

[0020] The other metal may be one or more atoms selected from the transition metals of Groups 3 to 11 of the periodic table and the typical metal elements of Groups 12 to 15. The other metal is preferably a transition metal element of Groups 3 to 11, more preferably a transition metal element of Groups 3 to 7, and even more preferably a transition metal element of Groups 4 to 6.

[0021] In one embodiment, the other metal is one or more atoms selected from Ta, Nb, Zr, Mo, W, Cr, Hf, Al, Ti and V.

[0022] In a preferred embodiment, the other metal is Ta, Nb, W, Mo, Cr or V.

[0023] In a more preferred embodiment, the other metal is Ta.

[0024] In one embodiment, the molar ratio of Si to the other metal is 10:90 to 99.9:0.1 (Si:other metal), preferably 10:90 to 99:1, more preferably 10:90 to 95:5, even more preferably 13:87 to 93:7, and particularly preferably 40:60 to 80:20, and may be, for example, 50:50 to 99:1, 50:50 to 90:10, or 75:25 to 99:1. By setting the molar ratio of Si to the other metal within this range, the durability of the surface treatment layer is improved. Furthermore, when the molar ratio of Si to the other metal varies with depth, the molar ratio of Si to the other metal in the intermediate layer may be the average value.

[0025] In one embodiment, the composition of the intermediate layer satisfies the above molar ratio in a region 0.1 to 10 nm, preferably 0.1 to 5 nm, more preferably 0.1 to 3 nm, and even more preferably 0.1 to 3 nm, or 0.1 to 2 nm from the outermost surface closest to the surface treatment layer. By setting the composition of the intermediate layer within the above molar ratio range, it is possible to more reliably improve wear resistance and chemical resistance.

[0026] In the above embodiment, the composition from the outermost surface to a predetermined depth may be the average value of the concentration from the outermost surface to a predetermined depth. For example, the average value of the composition from the outermost surface to 2 nm, 3 nm, or 5 nm may be the average value of the composition measured every predetermined time while sputtering at a constant speed for a predetermined period of time. For example, the composition of such an intermediate layer may be the average value of the concentration at 0.1 nm, 1 nm, 2 nm, 3 nm, 5 nm, 6 nm, 9 nm, and 10 nm from the outermost surface. For example, the composition of the intermediate layer from 0.1 to 10 nm from the outermost surface may be the average value of the concentration at 0.1 nm, 1 nm, 2 nm, 3 nm, 5 nm, 6 nm, 9 nm, and 10 nm from the outermost surface, and the composition of the intermediate layer from 0.1 to 5 nm from the outermost surface may be the average value of the concentration at 0.1 nm, 1 nm, 2 nm, 3 nm, and 5 nm from the outermost surface.

[0027] The thickness of the intermediate layer is not particularly limited, but may be, for example, 1.0 nm to 100 nm, preferably 2 nm to 50 nm, and more preferably 2 nm to 20 nm. By making the thickness of the intermediate layer 1.0 nm or more, the friction durability and chemical resistance of the surface treatment layer can be more reliably improved. Furthermore, by making the thickness of the intermediate layer 100 nm or less, the transparency of the article can be further improved.

[0028] The method for forming the intermediate layer is not particularly limited, but a method capable of simultaneously depositing Si and other metals is preferred. For example, sputtering, ion beam assist, vacuum deposition (preferably electron beam heating method), CVD (chemical vapor deposition), atomic layer deposition, etc. can be used, and sputtering is preferably used.

[0029] The sputtering method may be a DC (direct current) sputtering method, an AC (alternating current) sputtering method, an RF (radio frequency) sputtering method, an RAS (radical assisted) sputtering method, etc. These sputtering methods may be either a two-pole sputtering method or a magnetron sputtering method.

[0030] The silicon target used in sputtering is one whose main component is silicon (Si) or silicon oxide. It is desirable for a target whose main component is silicon (Si) to have a certain degree of conductivity so that DC sputtering is possible. Therefore, it is preferable to use a target whose main component is silicon (Si) made of polycrystalline silicon or single-crystal silicon doped with a known dopant such as phosphorus (P) or boron (B) within a range that does not impair the characteristics of the present invention. Such polycrystalline silicon targets and single-crystal silicon targets doped with phosphorus (P), boron (B), etc. can be used in any of DC sputtering, AC sputtering, RF sputtering, and RAS sputtering.

[0031] When forming a film by a sputtering method, a glass substrate is placed in a chamber filled with a mixed gas atmosphere of an inert gas and oxygen gas, and a target is selected as the adhesion layer forming material so as to have a desired composition, and a film is formed. At this time, the type of inert gas in the chamber is not particularly limited, and various inert gases such as argon and helium can be used.

[0032] The pressure inside the chamber containing the mixed gas of inert gas and oxygen gas is not particularly limited, but by setting it in the range of 0.5 Pa or less, it is easy to keep the surface roughness of the formed film within a preferred range. This is thought to be due to the following reason. That is, when the pressure inside the chamber containing the mixed gas of inert gas and oxygen gas is 0.5 Pa or less, the mean free path of the film-forming molecules is ensured, and the film-forming molecules reach the substrate with more energy. This is thought to promote rearrangement of the film-forming molecules, resulting in the formation of a film with a relatively dense and smooth surface. The lower limit of the pressure inside the chamber containing the mixed gas of inert gas and oxygen gas is not particularly limited, but it is desirable that it be 0.1 Pa or more, for example.

[0033] When forming the high refractive index layer and the low refractive index layer by sputtering, the thickness and composition of each layer can be adjusted, for example, by adjusting the discharge power, the film formation time, or the ratio of the mixed gas of inert gas and oxygen gas.

[0034] By providing the intermediate layer, the durability of the surface treatment layer can be improved. The durability refers to alkali resistance, hydrolysis resistance, and abrasion resistance.

[0035] From the viewpoint of alkali resistance, the molar ratio of Si to other metals is 10:90 to 99.9:0.1 (Si:other metals), preferably 10:90 to 99:1, more preferably 10:90 to 95:5, even more preferably 13:87 to 93:7, and particularly preferably 40:60 to 80:20, and may be, for example, 50:50 to 99:1, 50:50 to 90:10, or 75:25 to 99:1. By setting the molar ratio of Si to other metals within this range, the alkali resistance of the surface treatment layer is improved.

[0036] From the viewpoint of wear resistance, the molar ratio of Si to other metals is 10:90 to 99.9:0.1 (Si:other metals), preferably 10:90 to 99:1, more preferably 10:90 to 95:5, even more preferably 13:87 to 93:7, and particularly preferably 40:60 to 80:20, and may be, for example, 50:50 to 99:1, 50:50 to 90:10, or 75:25 to 99:1. By setting the molar ratio of Si to other metals within this range, the friction durability of the surface treatment layer is improved.

[0037] The composition and ratio of the intermediate layer can be determined by the following surface analysis, which can be performed by X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, or the like.

[0038] To measure the composition and ratio of the interlayer, an XPS (ULVAC-PHI) PHI5000 VersaProbe II can be used. XPS analysis conditions include a monochromated AlKα source at 25 W, a photoelectron detection area of ​​1400 μm x 300 μm, a photoelectron detection angle ranging from 20° to 90° (e.g., 20°, 45°, 90°), a pass energy of 23.5 eV, and Ar ions as sputter ions. Using the above equipment and measurement conditions, the peak areas of the C1s, O1s, F1s, Si2p orbitals, and appropriate orbitals of other metals can be observed, and the atomic ratios of carbon, oxygen, fluorine, silicon, and other metals can be calculated to determine the composition of the laminate. Suitable orbitals for other metals include, for example, 1s orbital for atomic number 5 (B), 2p orbital for atomic numbers 13-14, 21-31 (Al-Si, Sc-Ga), 3d orbital for atomic numbers 32-33, 39-52 (Ge-As, Y-Te), and 4f orbital for atomic numbers 72-83 (Hf-Bi).

[0039] It is also possible to analyze the depth direction of the intermediate layer. The measurement conditions for XPS analysis are a monochromated AlKα X-ray source at 25 W, a photoelectron detection area of ​​1400 μm × 300 μm, a photoelectron detection angle in the range of 20° to 90° (e.g., 20°, 45°, 90°), a pass energy of 23.5 eV, and Ar ions as sputtering ions. The surface layer of the laminate is etched by 1 to 100 nm in SiO2 equivalent by sputtering with Ar ions. At each etched depth, the peak areas of O1s, Si2p orbitals, and appropriate orbitals of other metals are observed, and the atomic ratios of oxygen, silicon, and other metals are calculated to determine the composition inside the laminate. Suitable orbitals for other metals include, for example, 1s orbital for atomic number 5 (B), 2p orbital for atomic numbers 13-14, 21-31 (Al-Si, Sc-Ga), 3d orbital for atomic numbers 32-33, 39-52 (Ge-As, Y-Te), and 4f orbital for atomic numbers 72-83 (Hf-Bi).

[0040] The detection depth can be adjusted appropriately by adjusting the photoelectron detection angle in the XPS analysis. For example, a shallow angle of approximately 20 degrees can achieve a detection depth of approximately 3 nm, while a deep angle of approximately 90 degrees can achieve a detection depth of approximately 10 nm.

[0041] Furthermore, when Si or the like is detected in the substrate in the composition analysis by XPS analysis, the amount of Si in the substrate detected can be calculated from the detected amount of specific atoms in the substrate, for example, if the substrate is glass, metal atoms (e.g., Al, Na, K, B, Ca, Mg, Sn, etc.) contained in trace amounts, and subtracted from the measurement results to calculate the composition of the intermediate layer.

[0042] The surface treatment layer is located directly above the intermediate layer, i.e., the surface treatment layer is formed so as to be in contact with the intermediate layer.

[0043] The surface treatment layer can be formed from a surface treatment agent containing a fluorine-containing silane compound.

[0044] The fluorine-containing silane compound is represented by the following formula (1) or (2): [ka] [In formula: R F1 independently in each occurrence, Rf 1 -R F -O q - and; R F2 is -Rf 2 p -R F -O q - and; Rf 1 each occurrence independently represents C optionally substituted by one or more fluorine atoms; 1-16 is an alkyl group; Rf 2 C optionally substituted with one or more fluorine atoms 1-6 is an alkylene group; R F is independently in each occurrence a divalent fluoropolyether group; p is 0 or 1; q is independently in each occurrence 0 or 1; R Si is independently in each occurrence a monovalent group containing a silicon atom to which is bonded a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group; At least one R Si is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded; X A are each independently a single bond or a divalent to decavalent organic group; α is an integer from 1 to 9; β is an integer from 1 to 9; Each γ is independently an integer of 1 to 9. The compound may be at least one fluoropolyether group-containing compound represented by the formula:

[0045] As used herein, the term "monovalent organic group" refers to a monovalent group containing carbon. The monovalent organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. A hydrocarbon group derivative refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain.

[0046] As used herein, the term "divalent organic group" is not particularly limited, but includes a divalent group in which one hydrogen atom has been further eliminated from a hydrocarbon group.

[0047] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, in which one hydrogen atom has been removed from the molecule. Examples of such hydrocarbon groups include, but are not limited to, hydrocarbon groups having 1 to 20 carbon atoms, which may be substituted with one or more substituents, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. The hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc., at its terminal or in the molecular chain.

[0048] As used herein, the substituent of the "hydrocarbon group" is not particularly limited, but examples thereof include a halogen atom; a C 1-6 Alkyl group, C 2-6 Alkenyl group, C 2-6 Alkynyl group, C 3-10 Cycloalkyl groups, C 3-10 Unsaturated cycloalkyl groups, 5-10 membered heterocyclyl groups, 5-10 membered unsaturated heterocyclyl groups, C 6-10 Examples include one or more groups selected from aryl groups and 5- to 10-membered heteroaryl groups.

[0049] In this specification, alkyl groups and phenyl groups may be unsubstituted or substituted unless otherwise specified. Substituents for such groups are not particularly limited, but include, for example, halogen atoms, C 1-6 Alkyl group, C 2-6 Alkenyl groups and C 2-6 alkynyl groups.

[0050] As used herein, the term "hydrolyzable group" refers to a group that can undergo a hydrolysis reaction, i.e., a group that can be removed from the main skeleton of a compound by a hydrolysis reaction. Examples of hydrolyzable groups include -OR h , -OCOR h , -ON=CR h 2, -NR h 2, -NHR h , halogen (wherein R h is a substituted or unsubstituted C 1-4 (representing an alkyl group) and the like.

[0051] In the above formula (1), R F1 independently in each occurrence, Rf 1 -R F -O q -It is.

[0052] In the above formula (2), R F2 is -Rf 2 p -R F -O q -It is.

[0053] In the above formula, Rf 1 each occurrence independently represents C optionally substituted by one or more fluorine atoms; 1-16 It is an alkyl group.

[0054] C optionally substituted with one or more fluorine atoms 1-16"C" in alkyl group 1-16 The "alkyl group" may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C 1-6 Alkyl groups, especially C 1-3 alkyl group, more preferably a straight-chain C 1-6 Alkyl groups, especially C 1-3 It is an alkyl group.

[0055] Above Rf 1 is preferably C substituted by one or more fluorine atoms 1-16 alkyl group, more preferably CF2H-C 1-15 A perfluoroalkylene group, more preferably C 1-16 It is a perfluoroalkyl group.

[0056] Above C 1-16 The perfluoroalkyl group may be a straight or branched chain, and is preferably a straight or branched C 1-6 Perfluoroalkyl groups, especially C 1-3 A perfluoroalkyl group, more preferably a linear C 1-6 Perfluoroalkyl groups, especially C 1-3 A perfluoroalkyl group, specifically -CF3, -CF2CF3, or -CF2CF2CF3.

[0057] In the above formula, Rf 2 C optionally substituted with one or more fluorine atoms 1-6 It is an alkylene group.

[0058] C optionally substituted with one or more fluorine atoms 1-6 "C" in the alkylene group 1-6 The "alkylene group" may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C 1-3 It is preferably a linear alkylene group. 1-3 It is an alkylene group.

[0059] Above Rf 2is preferably C substituted by one or more fluorine atoms 1-6 is an alkylene group, more preferably C 1-6 A perfluoroalkylene group, more preferably C 1-3 It is a perfluoroalkylene group.

[0060] Above C 1-6 The perfluoroalkylene group may be a straight chain or a branched chain, and is preferably a straight chain or branched C 1-3 A perfluoroalkylene group, more preferably a linear C 1-3 A perfluoroalkylene group, specifically, -CF2-, -CF2CF2-, or -CF2CF2CF2-.

[0061] In the above formula, p is 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.

[0062] In the above formula, q is, independently at each occurrence, 0 or 1. In one embodiment, q is 0. In another embodiment, q is 1.

[0063] Above R F1 and R F2 In R F is independently in each occurrence a divalent fluoropolyether group.

[0064] R F is preferably of the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - [In formula: R Fa is independently in each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom; a, b, c, d, e, and f each independently represent an integer of 0 to 200, and the sum of a, b, c, d, e, and f is 1 or more. The repeating units enclosed in parentheses with a, b, c, d, e, or f may be present in any order in the formula.] It is a group represented by the following formula:

[0065] R Fa is preferably a hydrogen atom or a fluorine atom, and more preferably a fluorine atom.

[0066] Preferably, a, b, c, d, e and f may each independently be an integer of 0 to 100.

[0067] The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. The sum of a, b, c, d, e, and f is preferably 200 or less, more preferably 100 or less, and even more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

[0068] The repeating units enclosed in parentheses with the above-mentioned a, b, c, d, e and f may be linear or branched.

[0069] With respect to the repeating units enclosed in parentheses with a, b, c, d, e and f above, -(OC6F 12 )- can be -(OCF2CF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. 10)- can be -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- can be -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, or -(OCF2CF(C2F5))-. -(OC3F6)- (i.e., in the above formula, R Fa is a fluorine atom) can be -(OCFCFCF)-, -(OCF(CF)CF)-, or -(OCFCF(CF))-. -(OCF)- can be -(OCFCF)- or -(OCF(CF))-.

[0070] In one embodiment, the repeating unit is linear, i.e., -(OCF 12 )- is -(OCF2CF2CF2CF2CF2CF2CF2)-, and -(OC5F 10 )- is -(OCF2CF2CF2CF2CF2)-, -(OC4F8)- is -(OCF2CF2CF2CF2)-, -(OC3F6)- is -(OCF2CF2CF2)-, and -(OC2F4)- is -(OCF2CF2)-. By making the repeating units linear, the slip properties of the surface treatment layer are improved.

[0071] In one embodiment, the repeating unit is branched. By making the repeating unit branched, the dynamic friction coefficient of the surface treatment layer can be increased.

[0072] In one embodiment, R F are each independently represented by the following formulas (f1) to (f4) in each occurrence: -(OC3F6) d - (f1) [In the formula, d is an integer of 1 to 200.] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2) [In the formula, c and d each independently represent an integer of 0 or more and 30 or less, and e and f each independently represent an integer of 1 or more and 200 or less, the sum of c, d, e, and f is 2 or more, The order of occurrence of each repeating unit enclosed in parentheses with the subscript c, d, e, or f is arbitrary in the formula.] -(R 6 -R 7 ) g - (f3) [In the formula, R 6 is OCF2 or OC2F4, R 7 are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups; and g is an integer from 2 to 100. -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f4) [In the formula, e is an integer of 1 or more and 200 or less, a, b, c, d, and f are each independently an integer of 0 or more and 200 or less, the sum of a, b, c, d, e, and f is at least 1, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6)d -(OC2F4) e -(OCF2) f - (f5) [In the formula, f is an integer of 1 or more and 200 or less, a, b, c, d, and e are each independently an integer of 0 or more and 200 or less, the sum of a, b, c, d, e, and f is at least 1, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] It is a group represented by the following formula:

[0073] In the above formula (f1), d is preferably an integer of 5 to 200, more preferably 10 to 100, and even more preferably 15 to 50, for example, an integer of 25 to 35. The above formula (f1) is preferably -(OCF2CF2CF2) d -or-(OCF(CF3)CF2) d -, and more preferably -(OCF2CF2CF2) d - is a group represented by the formula:

[0074] In the formula (f2), e and f are each independently an integer of preferably 5 or more and 200 or less, more preferably 10 to 200. The sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. In one embodiment, the formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f In another embodiment, formula (f2) is a group represented by -(OC2F4) e -(OCF2) f It may also be a group represented by the formula -.

[0075] In the above formula (f3), R 6 is preferably OC2F4. In the above (f3), R 7is preferably a group selected from OC2F4, OC3F6 and OC4F8, or a combination of two or three groups independently selected from these groups, more preferably a group selected from OC3F6 and OC4F8. The combination of two or three groups independently selected from OC2F4, OC3F6 and OC4F8 is not particularly limited, and examples thereof include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC Examples include 2F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4-, and -OC4F8OC2F4OC2F4-. In the above formula (f3), g is preferably an integer of 3 or more, more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 may be either a straight chain or a branched chain, and is preferably a straight chain. In this embodiment, the above formula (f3) is preferably -(OC2F4-OC3F6) g -or-(OC2F4-OC4F8) g -It is.

[0076] In the above formula (f4), e is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less. The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

[0077] In the above formula (f5), f is preferably an integer of 1 or more and 100 or less, more preferably an integer of 5 or more and 100 or less. The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

[0078] In one embodiment, the R F is a group represented by the above formula (f1).

[0079] In one embodiment, the R F is a group represented by the above formula (f2).

[0080] In one embodiment, the R F is a group represented by the above formula (f3).

[0081] In one embodiment, the R F is a group represented by the above formula (f4).

[0082] In one embodiment, the R F is a group represented by the above formula (f5).

[0083] Above R F In the formula, the ratio of e to f (hereinafter referred to as "e / f ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, even more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85. By setting the e / f ratio to 10 or less, the slipperiness, friction durability, and chemical resistance (e.g., durability against artificial sweat) of the surface treatment layer obtained from this compound are further improved. The smaller the e / f ratio, the more improved the slipperiness and friction durability of the surface treatment layer. On the other hand, by setting the e / f ratio to 0.1 or more, the stability of the compound can be further improved. The larger the e / f ratio, the more improved the stability of the compound.

[0084] In one embodiment, the e / f ratio is preferably 0.2 to 0.95, and more preferably 0.2 to 0.9.

[0085] In one embodiment, from the viewpoint of heat resistance, the e / f ratio is preferably 1.0 or more, and more preferably 1.0 to 2.0.

[0086] In the above fluoropolyether group-containing compound, R F1 and R F2 The number average molecular weight of the R moiety is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. F1 and R F2 The number average molecular weight of 19 The value is measured by F-NMR.

[0087] In another embodiment, R F1 and R F2 The number average molecular weight of the moiety may be from 500 to 30,000, preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000, even more preferably from 2,000 to 10,000, for example from 3,000 to 6,000.

[0088] In another embodiment, R F1 and R F2 The number average molecular weight of the moiety can be from 4,000 to 30,000, preferably from 5,000 to 10,000, and more preferably from 6,000 to 10,000.

[0089] In the above formulas (1) and (2), R Si is independently in each occurrence a hydroxyl group, a hydrolyzable group, a monovalent group containing a silicon atom to which a hydrogen atom or a monovalent organic group is bonded, and at least one R Si is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

[0090] In a preferred embodiment, R Si is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

[0091] In a preferred embodiment, R Si is expressed by the following formula (S1), (S2), (S3), or (S4): [ka] It is a group represented by the following formula:

[0092] In the above formula, R 11 is independently at each occurrence a hydroxyl group or a hydrolyzable group.

[0093] R 11 is preferably, independently at each occurrence, a hydrolyzable group.

[0094] R 11 is preferably, independently at each occurrence, -OR h , -OCOR h , -ON=CR h 2, -NR h 2, -NHR h or halogen (wherein R h is a substituted or unsubstituted C 1-4 alkyl group), and more preferably -OR h (i.e., an alkoxy group). h Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, with methyl or ethyl groups being more preferred. In one embodiment, R h is a methyl group, and in another embodiment, R h is an ethyl group.

[0095] In the above formula, R 12 is independently in each occurrence a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0096] R 12 In the formula, the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0097] In the above formula, n1 is (SiR11 n1 R 12 3-n1 ) units are each independently an integer of 0 to 3, provided that R Si is a group represented by formula (S1) or (S2), R at the end of formula (1) and formula (2) Si β and R Si γ In the moiety (hereinafter also simply referred to as the "terminal moiety" of formula (1) and formula (2)), n1 is 1 to 3 (SiR 11 n1 R 12 3-n1 ) unit is present. That is, in such a terminal portion, all n1s do not simultaneously become 0. In other words, in the terminal portion of formula (1) and formula (2), there is at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

[0098] n1 is (SiR 11 n1 R 12 3-n1 ) units are each independently an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0099] In the above formula, X 11 is independently in each occurrence a single bond or a divalent organic group. Such a divalent organic group is preferably C 1-20 It is an alkylene group. 1-20 The alkylene group may be straight-chain or branched, but is preferably straight-chain.

[0100] In a preferred embodiment, X 11 each occurrence independently represents a single bond or a straight-chain C 1-6 Alkylene group, preferably a single bond or a straight chain C 1-3 Alkylene group, more preferably a single bond or a straight chain C 1-2 It is preferably a linear C alkylene group. 1-2 It is an alkylene group.

[0101] In the above formula, R 13 is independently in each occurrence a hydrogen atom or a monovalent organic group. Such a monovalent organic group is preferably C 1-20 It is an alkyl group. 1-20 The alkyl group may be straight-chain or branched, but is preferably straight-chain.

[0102] In a preferred embodiment, R 13 each occurrence independently represents a hydrogen atom or a straight-chain C 1-6 is an alkyl group, preferably a hydrogen atom or a straight-chain C 1-3 It is an alkyl group, preferably a hydrogen atom or a methyl group.

[0103] In the above formula, t is independently an integer of 2 to 10 in each occurrence.

[0104] In a preferred embodiment, t is independently an integer from 2 to 6 in each occurrence.

[0105] In the above formula, R 14 is independently in each occurrence a hydrogen atom or a halogen atom. Such a halogen atom is preferably an iodine atom, a chlorine atom, or a fluorine atom, more preferably a fluorine atom. In a preferred embodiment, R 14 is a hydrogen atom.

[0106] In the above formula, R a1 independently in each occurrence -Z 1 -SiR 21 p1 R 22 q1 R 23 r1 is.

[0107] Above Z 1 In each occurrence, each independently represents an oxygen atom or a divalent organic group. 1 The structure written as 21 p1 R22 q1 R 23 r1 )

[0108] In a preferred embodiment, Z 1 is a divalent organic group.

[0109] In a preferred embodiment, Z 1 is Z 1 Preferably, in formula (S3), (Si-Z) does not include a compound that forms a siloxane bond with the Si atom to which (Si-Z) is bonded. 1 -Si does not contain a siloxane bond.

[0110] Above Z 1 is preferably C 1-6 Alkylene group, -(CH2) z1 -O-(CH2) z2 - (wherein z1 is an integer of 0 to 6, for example, an integer of 1 to 6, and z2 is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH2) z3 -phenylene-(CH2) z4 - (wherein z3 is an integer of 0 to 6, for example, an integer of 1 to 6, and z4 is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene group may be straight-chain or branched, but is preferably straight-chain. These groups may contain, for example, fluorine atoms, C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0111] In one embodiment, Z 1 is C 1-6 Alkylene group or -(CH2) z3 -phenylene-(CH2) z4 -, preferably -phenylene-(CH2) z4 -It is. Z 1 is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.

[0112] In another embodiment, the Z 1 is C 1-3 In one embodiment, Z is an alkylene group. 1 can be -CH2CH2CH2-. In another embodiment, Z 1 can be -CH2CH2-.

[0113] Above R 21 independently in each occurrence -Z 1’ -SiR 21’ p1’ R 22’ q1’ R 23’ r1’ is.

[0114] Above Z 1’ In each occurrence, each independently represents an oxygen atom or a divalent organic group. 1’ The structure written as 21’ p1’ R 22’ q1’ R 23’ r1’ )

[0115] In a preferred embodiment, Z 1’ is a divalent organic group.

[0116] In a preferred embodiment, Z 1’ is Z 1’ Preferably, in formula (S3), (Si-Z) does not include a compound that forms a siloxane bond with the Si atom to which (Si-Z) is bonded. 1’ —Si) does not contain a siloxane bond.

[0117] Above Z 1’ is preferably C 1-6 Alkylene group, -(CH2) z1’ -O-(CH2) z2’ - (wherein z1' is an integer of 0 to 6, for example, an integer of 1 to 6, and z2' is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH2) z3’ -phenylene-(CH2) z4’- (wherein z3' is an integer of 0 to 6, for example, an integer of 1 to 6, and z4' is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene group may be straight-chain or branched, but is preferably straight-chain. These groups may contain, for example, fluorine atoms, C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0118] In one embodiment, Z 1’ is C 1-6 Alkylene group or -(CH2) z3’ -phenylene-(CH2) z4’ -, preferably -phenylene-(CH2) z4’ -It is. Z 1’ is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.

[0119] In another embodiment, the Z 1’ is C 1-3 In one embodiment, Z is an alkylene group. 1’ can be -CH2CH2CH2-. In another embodiment, Z 1’ can be -CH2CH2-.

[0120] Above R 21’ independently in each occurrence -Z 1” -SiR 22” q1” R 23” r1” is.

[0121] Above Z 1” In each occurrence, each independently represents an oxygen atom or a divalent organic group. 1” The structure written as 22” q1” R 23” r1” )

[0122] In a preferred embodiment, Z 1” is a divalent organic group.

[0123] In a preferred embodiment, Z 1” is Z 1” Preferably, in formula (S3), (Si-Z) does not include a compound that forms a siloxane bond with the Si atom to which (Si-Z) is bonded. 1” —Si) does not contain a siloxane bond.

[0124] Above Z 1” is preferably C 1-6 Alkylene group, -(CH2) z1” -O-(CH2) z2” - (wherein z1" is an integer of 0 to 6, for example, an integer of 1 to 6, and z2" is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH2) z3” -phenylene-(CH2) z4” - (wherein z3" is an integer of 0 to 6, for example, an integer of 1 to 6, and z4" is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene group may be straight-chain or branched, but is preferably straight-chain. These groups may contain, for example, fluorine atoms, C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0125] In one embodiment, Z 1” is C 1-6 Alkylene group or -(CH2) z3” -phenylene-(CH2) z4” -, preferably -phenylene-(CH2) z4” -It is. Z 1” is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.

[0126] In another embodiment, the Z 1” is C 1-3 In one embodiment, Z is an alkylene group. 1”can be -CH2CH2CH2-. In another embodiment, Z 1” can be -CH2CH2-.

[0127] Above R 22” is independently at each occurrence a hydroxyl group or a hydrolyzable group.

[0128] R 22” is preferably, independently at each occurrence, a hydrolyzable group.

[0129] R 22” is preferably, independently at each occurrence, -OR h , -OCOR h , -ON=CR h 2, -NR h 2, -NHR h or halogen (wherein R h is a substituted or unsubstituted C 1-4 alkyl group), and more preferably -OR h (i.e., an alkoxy group). h Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, with methyl or ethyl groups being more preferred. In one embodiment, R h is a methyl group, and in another embodiment, R h is an ethyl group.

[0130] Above R 23” is independently in each occurrence a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0131] R 23” In the formula, the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0132] The above q1" is independently an integer of 0 to 3 in each occurrence, and the above r1" is independently an integer of 0 to 3 in each occurrence. The sum of q1" and r1" is (SiR 22” q1” R 23” r1” ) units, it is 3.

[0133] q1” is (SiR 22” q1” R 23” r1” ) units are each independently an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0134] Above R 22’ is independently at each occurrence a hydroxyl group or a hydrolyzable group.

[0135] R 22’ is preferably, independently at each occurrence, a hydrolyzable group.

[0136] R 22’ is preferably, independently at each occurrence, -OR h , -OCOR h , -ON=CR h 2, -NR h 2, -NHR h or halogen (wherein R h is a substituted or unsubstituted C 1-4 alkyl group), and more preferably -OR h (i.e., an alkoxy group). h Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, with methyl or ethyl groups being more preferred. In one embodiment, R h is a methyl group, and in another embodiment, R h is an ethyl group.

[0137] Above R 23’ is independently in each occurrence a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0138] R 23’ In the formula, the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0139] The above p1' is independently an integer of 0 to 3 in each occurrence, q1' is independently an integer of 0 to 3 in each occurrence, and r1' is independently an integer of 0 to 3 in each occurrence. The sum of p', q1', and r1' is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ ) units, it is 3.

[0140] In one embodiment, p1' is 0.

[0141] In one embodiment, p1′ is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ ) units may each independently be an integer of 1 to 3, an integer of 2 to 3, or 3. In a preferred embodiment, p1' is 3.

[0142] In one embodiment, q1′ is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ ) units are each independently an integer of 1 to 3, preferably an integer of 2 or 3, and more preferably 3.

[0143] In one embodiment, p1' is 0 and q1' is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ ) units are each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.

[0144] Above R 22 is independently at each occurrence a hydroxyl group or a hydrolyzable group.

[0145] R 22 is preferably, independently at each occurrence, a hydrolyzable group.

[0146] R 22 is preferably, independently at each occurrence, -OR h , -OCOR h , -ON=CR h 2, -NR h 2, -NHR h or halogen (wherein R h is a substituted or unsubstituted C 1-4 alkyl group), and more preferably -OR h (i.e., an alkoxy group). h Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, with methyl or ethyl groups being more preferred. In one embodiment, R h is a methyl group, and in another embodiment, R h is an ethyl group.

[0147] Above R 23 is independently in each occurrence a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0148] R 23In the formula, the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0149] The above p1 is independently an integer of 0 to 3 in each occurrence, q1 is independently an integer of 0 to 3 in each occurrence, and r1 is independently an integer of 0 to 3 in each occurrence. The sum of p, q1, and r1 is (SiR 21 p1 R 22 q1 R 23 r1 ) units, it is 3.

[0150] In one embodiment, p1 is 0.

[0151] In one embodiment, p1 is (SiR 21 p1 R 22 q1 R 23 r1 ) units may each independently be an integer of 1 to 3, an integer of 2 to 3, or 3. In a preferred embodiment, p1 is 3.

[0152] In one embodiment, q1 is (SiR 21 p1 R 22 q1 R 23 r1 ) units are each independently an integer of 1 to 3, preferably an integer of 2 or 3, and more preferably 3.

[0153] In one embodiment, p1 is 0 and q1 is (SiR 21 p1 R 22 q1 R 23 r1 ) units are each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.

[0154] In the above formula, Rb1 is independently at each occurrence a hydroxyl group or a hydrolyzable group.

[0155] R b1 is preferably, independently at each occurrence, a hydrolyzable group.

[0156] R b1 is preferably, independently at each occurrence, -OR h , -OCOR h , -ON=CR h 2, -NR h 2, -NHR h or halogen (wherein R h is a substituted or unsubstituted C 1-4 alkyl group), and more preferably -OR h (i.e., an alkoxy group). h Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, with methyl or ethyl groups being more preferred. In one embodiment, R h is a methyl group, and in another embodiment, R h is an ethyl group.

[0157] In the above formula, R c1 is independently in each occurrence a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0158] R c1 In the formula, the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0159] The above k1 is independently an integer of 0 to 3 in each occurrence, l1 is independently an integer of 0 to 3 in each occurrence, and m1 is independently an integer of 0 to 3 in each occurrence. The sum of p, l1, and m1 is (SiR a1 k1 R b1 l1 R c1 m1 ) units, it is 3.

[0160] In one embodiment, k1 is (SiR a1 k1 R b1 l1 R c1 m1 ) units are each independently an integer of 1 to 3, preferably 2 or 3, more preferably 3. In a preferred embodiment, k1 is 3.

[0161] In the above formulas (1) and (2), R Si When is a group represented by formula (S3), preferably, at least two Si atoms having hydroxyl groups or hydrolyzable groups bonded thereto are present in the terminal portions of formula (1) and formula (2).

[0162] In a preferred embodiment, the group represented by formula (S3) is -Z 1 -SiR 22 q1 R 23 r1 (wherein q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1 is an integer of 0 to 2), -Z 1’ -SiR 22’ q1’ R 23’ r1’ (wherein q1' is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1' is an integer of 0 to 2), or -Z 1” -SiR 22” q1” R 23” r1”(wherein q1″ is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1″ is an integer of 0 to 2).

[0163] In a preferred embodiment, in formula (S3), R 21’ When present, at least one, preferably all, R 21’ In the formula, q1″ is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0164] In a preferred embodiment, in formula (S3), R 21 When present, at least one, preferably all, R 21 In the formula (I), p1' is 0, and q1' is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0165] In a preferred embodiment, in formula (S3), R a1 When present, at least one, preferably all, R a1 In the formula (I), p1 is 0, and q1 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0166] In a preferred embodiment, in formula (S3), k1 is 2 or 3, preferably 3; p1 is 0; and q1 is 2 or 3, preferably 3.

[0167] R d1 independently in each occurrence -Z 2 -CR 31 p2 R 32 q2 R 33 r2 is.

[0168] Z 2 In each occurrence, each independently represents a single bond, an oxygen atom, or a divalent organic group. 2 The structure written as (CR 31 p2 R 32q2 R 33 r2 )

[0169] In a preferred embodiment, Z 2 is a divalent organic group.

[0170] Above Z 2 is preferably C 1-6 Alkylene group, -(CH2) z5 -O-(CH2) z6 - (wherein z5 is an integer of 0 to 6, for example, an integer of 1 to 6, and z6 is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH2) z7 -phenylene-(CH2) z8 - (wherein z7 is an integer of 0 to 6, for example, an integer of 1 to 6, and z8 is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene group may be straight-chain or branched, but is preferably straight-chain. These groups may contain, for example, fluorine atoms, C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0171] In one embodiment, Z 2 is C 1-6 Alkylene group or -(CH2) z7 -phenylene-(CH2) z8 -, preferably -phenylene-(CH2) z8 -It is. Z 2 is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.

[0172] In another embodiment, the Z 2 is C 1-3 In one embodiment, Z is an alkylene group. 2 can be -CH2CH2CH2-. In another embodiment, Z 2 can be -CH2CH2-.

[0173] R 31 independently in each occurrence -Z 2’ -CR 32’ q2’ R 33’ r2’ is.

[0174] Z 2’ In each occurrence, each independently represents a single bond, an oxygen atom, or a divalent organic group. 2’ The structure written as (CR 32’ q2’ R 33’ r2’ )

[0175] Above Z 2’ is preferably C 1-6 Alkylene group, -(CH2) z5’ -O-(CH2) z6’ - (wherein z5' is an integer of 0 to 6, for example, an integer of 1 to 6, and z6' is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH2) z7’ -phenylene-(CH2) z8’ - (wherein z7' is an integer of 0 to 6, for example, an integer of 1 to 6, and z8' is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene group may be straight-chain or branched, but is preferably straight-chain. These groups may contain, for example, fluorine atoms, C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0176] In one embodiment, Z 2’ is C 1-6 Alkylene group or -(CH2) z7’ -phenylene-(CH2) z8’ -, preferably -phenylene-(CH2) z8’ -It is. Z 2’ is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.

[0177] In another embodiment, the Z 2’ is C 1-3 In one embodiment, Z is an alkylene group. 2’ can be -CH2CH2CH2-. In another embodiment, Z 2’ can be -CH2CH2-.

[0178] Above R 32’ independently in each occurrence -Z 3 -SiR 34 n2 R 35 3-n2 is.

[0179] Above Z 3 In each occurrence, each independently represents a single bond, an oxygen atom, or a divalent organic group. 3 The structure written as 34 n2 R 35 3-n2 )

[0180] In one embodiment, Z 3 is an oxygen atom.

[0181] In one embodiment, Z 3 is a divalent organic group.

[0182] Above Z 3 is preferably C 1-6 Alkylene group, -(CH2) z5” -O-(CH2) z6” - (wherein z5" is an integer of 0 to 6, for example, an integer of 1 to 6, and z6" is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH2) z7” -phenylene-(CH2) z8” - (wherein z7" is an integer of 0 to 6, for example, an integer of 1 to 6, and z8" is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene group may be straight-chain or branched, but is preferably straight-chain. These groups may contain, for example, fluorine atoms, C1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0183] In one embodiment, Z 3 is C 1-6 Alkylene group or -(CH2) z7” -phenylene-(CH2) z8” -, preferably -phenylene-(CH2) z8” -It is. Z 3 is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.

[0184] In another embodiment, the Z 3 is C 1-3 In one embodiment, Z is an alkylene group. 3 can be -CH2CH2CH2-. In another embodiment, Z 3 can be -CH2CH2-.

[0185] Above R 34 is independently at each occurrence a hydroxyl group or a hydrolyzable group.

[0186] R 34 is preferably, independently at each occurrence, a hydrolyzable group.

[0187] R 34 is preferably, independently at each occurrence, -OR h , -OCOR h , -ON=CR h 2, -NR h 2, -NHR h or halogen (wherein R h is a substituted or unsubstituted C 1-4 alkyl group), and more preferably -OR h (i.e., an alkoxy group). hExamples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, with methyl or ethyl groups being more preferred. In one embodiment, R h is a methyl group, and in another embodiment, R h is an ethyl group.

[0188] Above R 35 is independently in each occurrence a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0189] R 35 In the formula, the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0190] In the above formula, n2 is (SiR 34 n2 R 35 3-n2 ) units are each independently an integer of 0 to 3, provided that R Si is a group represented by formula (S4), n2 is 1 to 3 in the terminal portion of formula (1) and formula (2) (SiR 34 n2 R 35 3-n2 ) unit is present. That is, in such a terminal portion, all n2s do not simultaneously become 0. In other words, in the terminal portion of formula (1) and formula (2), there is at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

[0191] n2 is (SiR 34 n2 R 35 3-n2 ) units are each independently an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0192] Above R 33’ is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0193] R 33’ In the formula, the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0194] In one embodiment, R 33’ is a hydroxyl group.

[0195] In another embodiment, R 33’ The monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is an alkyl group.

[0196] The above q2' is independently an integer of 0 to 3 in each occurrence, and the above r2' is independently an integer of 0 to 3 in each occurrence. The sum of q2' and r2' is (SiR 32’ q2’ R 33’ r2’ ) units, it is 3.

[0197] q2' is (SiR 32’ q2’ R 33’ r2’ ) units are each independently an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0198] R 32 independently in each occurrence -Z 3 -SiR 34 n2 R 35 3-n2 It takes -Z 3 -SiR 34 n2 R 35 3-n2is the above R 32’ This has the same meaning as the description in

[0199] Above R 33 is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0200] R 33 In the formula, the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0201] In one embodiment, R 33 is a hydroxyl group.

[0202] In another embodiment, R 33 The monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is an alkyl group.

[0203] The above p2 is independently an integer of 0 to 3 in each occurrence, q2 is independently an integer of 0 to 3 in each occurrence, and r2 is independently an integer of 0 to 3 in each occurrence. The sum of p2, q2, and r2 is (CR 31 p2 R 32 q2 R 33 r2 ) units, it is 3.

[0204] In one embodiment, p2 is 0.

[0205] In one embodiment, p2 is (CR 31 p2 R 32 q2 R 33 r2 ) units may each independently be an integer of 1 to 3, an integer of 2 to 3, or 3. In a preferred embodiment, p2 is 3.

[0206] In one embodiment, q2 is (CR 31 p2 R 32 q2 R 33 r2 ) units are each independently an integer of 1 to 3, preferably an integer of 2 or 3, and more preferably 3.

[0207] In one embodiment, p2 is 0 and q2 is (CR 31 p2 R 32 q2 R 33 r2 ) units are each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.

[0208] R e1 independently in each occurrence -Z 3 -SiR 34 n2 R 35 3-n2 It takes -Z 3 -SiR 34 n2 R 35 3-n2 is the above R 32’ This has the same meaning as the description in

[0209] R f1 is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0210] R f1 In the formula, the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0211] In one embodiment, R f1 is a hydroxyl group.

[0212] In another embodiment, R f1 The monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is an alkyl group.

[0213] The above k2 is independently an integer of 0 to 3 in each occurrence, l2 is independently an integer of 0 to 3 in each occurrence, and m2 is independently an integer of 0 to 3 in each occurrence. The sum of k2, l2, and m2 is (CR d1 k2 R e1 l2 R f1 m2 ) units, it is 3.

[0214] In one embodiment, R Si is a group represented by formula (S4), n2 is 1 to 3, preferably 2 or 3, and more preferably 3 (SiR 34 n2 R 35 3-n2 ) units are present at each terminal portion of formula (1) and formula (2) by two or more, for example, 2 to 27, preferably 2 to 9, more preferably 2 to 6, even more preferably 2 to 3, and particularly preferably 3.

[0215] In a preferred embodiment, in formula (S4), R 32’ When present, at least one, preferably all, R 32’ In the formula, n2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0216] In a preferred embodiment, in formula (S4), R 32 When present, at least one, preferably all, R 32 In the formula, n2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0217] In a preferred embodiment, in formula (S4), R e1 When present, at least one, preferably all, Re1 In the formula, n2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0218] In a preferred embodiment, in formula (S4), k2 is 0, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3.

[0219] In one embodiment, R Si is a group represented by formula (S2), (S3) or (S4).

[0220] In one embodiment, R Si is a group represented by formula (S1), (S3) or (S4).

[0221] In one embodiment, R Si is a group represented by formula (S3) or (S4).

[0222] In one embodiment, R Si is a group represented by formula (S1).

[0223] In one embodiment, R Si is a group represented by formula (S2).

[0224] In one embodiment, R Si is a group represented by formula (S3).

[0225] In one embodiment, R Si is a group represented by formula (S4).

[0226] In the above formulas (1) and (2), X A The fluoropolyether moiety (R) mainly provides water repellency and surface slipperiness. F1 and R F2 ) and the substrate. Si ) and the linker. Amay be a single bond or any other group, so long as the compounds represented by formulas (1) and (2) can exist stably.

[0227] In the above formula (1), α is an integer of 1 to 9, and β is an integer of 1 to 9. These α and β are X A The sum of α and β can vary depending on the valence of X A For example, X A When X is a decavalent organic group, the sum of α and β is 10, and for example, α can be 9 and β can be 1, α can be 5 and β can be 5, or α can be 1 and β can be 9. A When is a divalent organic group, α and β are 1.

[0228] In the above formula (2), γ is an integer of 1 to 9. γ is X A That is, γ can vary depending on the valence of X A is the valence of the element minus 1.

[0229] X A are each independently a single bond or a divalent to decavalent organic group.

[0230] Above X A The divalent to decavalent organic group in the formula (I) is preferably a divalent to octavalent organic group. In one embodiment, the divalent to decavalent organic group is preferably a divalent to tetravalent organic group, more preferably a divalent organic group. In another embodiment, the divalent to decavalent organic group is preferably a trivalent to octavalent organic group, more preferably a trivalent to hexavalent organic group.

[0231] In one embodiment, X A is a single bond or a divalent organic group, α is 1, and β is 1.

[0232] In one embodiment, X A is a single bond or a divalent organic group, and γ is 1.

[0233] In one embodiment, X Ais a trivalent to hexavalent organic group, α is 1, and β is 2 to 5.

[0234] In one embodiment, X A is a trivalent to hexavalent organic group, and γ is 2 to 5.

[0235] In one embodiment, X A is a trivalent organic group, α is 1, and β is 2.

[0236] In one embodiment, X A is a trivalent organic group and γ is 2.

[0237] X A When is a single bond or a divalent organic group, formulas (1) and (2) are represented by the following formulas (1') and (2'). [ka]

[0238] In one embodiment, X A is a single bond.

[0239] In another embodiment, X A is a divalent organic group.

[0240] In one embodiment, X A Examples of the group include a single bond and the group represented by the following formula: -(R 51 ) p5 -(X 51 ) q5 - [In formula: R 51 is a single bond, -(CH2) s5 - or an o-, m- or p-phenylene group, preferably -(CH2) s5 - and s5 is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2; X 51 is -(X 52 )l5 - represents X 52 each occurrence independently represents an -O-, -S-, o-, m-, or p-phenylene group, -C(O)O-, -Si(R 53 )2-, -(Si(R 53 )2O) m5 -Si(R 53 )2-, -CONR 54 -, -O-CONR 54 -, -NR 54 - and -(CH2) n5 represents a group selected from the group consisting of - R 53 independently in each occurrence a phenyl group, C 1-6 Alkyl group or C 1-6 represents an alkoxy group, preferably a phenyl group or C 1-6 is an alkyl group, more preferably a methyl group; R 54 are each independently in each occurrence a hydrogen atom, a phenyl group or C 1-6 represents an alkyl group (preferably a methyl group), m5 in each occurrence is independently an integer of 1 to 100, preferably an integer of 1 to 20; n5, in each occurrence, is independently an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3; l5 is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, p5 is 0 or 1, q5 is 0 or 1, wherein at least one of p5 and q5 is 1, and the repeating units enclosed in parentheses with p5 or q5 may be present in any order. Here, R A (Typically R A hydrogen atoms) are fluorine atoms, C 1-3 Alkyl groups and C 1-3 In a preferred embodiment, RA is not substituted with these groups.

[0241] In a preferred embodiment, the X A are each independently -(R 51 ) p5 -(X 51 ) q5 -R 56 -R 56 is a single bond, -(CH2) t5 - or an o-, m- or p-phenylene group, preferably -(CH2) t5 t5 is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. Here, R 56 (Typically R 56 hydrogen atoms) are fluorine atoms, C 1-3 Alkyl groups and C 1-3 In a preferred embodiment, R 56 is not substituted with these groups.

[0242] Preferably, the above X A are each independently single bond, -X f5 -C 1-20 an alkylene group, -X f5 -R 51 -X 53 -R 52 -,or -X f5 -X 54 -R 5 - [In the formula, R 51 and R 52 has the same meaning as above, X 53 teeth, -O-, -S-, -C(O)O-, -CONR 54 -, -O-CONR 54 -, -Si(R 53 )2-, -(Si(R 53 )2O) m5 -Si(R 53 )2-, -O-(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2-, -O-(CH2) u5 -Si(R 53 )2-O-Si(R 53 )2-CH2CH2-Si(R 53 )2-O-Si(R 53 )2-, -O-(CH2) u5 -Si(OCH3)2OSi(OCH3)2-, -CONR 54 -(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2-, -CONR 54 -(CH2) u5 -N(R 54 )-,or -CONR 54 -(o-, m- or p-phenylene)-Si(R 53 )2- (In the formula, R 53 , R 54 and m5 are as defined above, u5 represents an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 or 3; X 54 teeth, -S-, -C(O)O-, -CONR 54 -, -O-CONR 54 -, -CONR 54 -(CH2) u5 -(Si(R 54 )2O) m5 -Si(R 54 )2-, -CONR54 -(CH2) u5 -N(R 54 )-,or -CONR 54 -(o-, m- or p-phenylene)-Si(R 54 )2- (In the formula, each symbol has the same meaning as above.) represents X f5 represents a single bond or a perfluoroalkylene group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 to 2 carbon atoms, such as a difluoromethylene group.] It could be.

[0243] More preferably, the above X A are each independently single bond, -X f5 -C 1-20 an alkylene group, -X f5 -(CH2) s5 -X 53 -, -X f5 -(CH2) s5 -X 53 -(CH2) t5 - -X f5 -X 54 -,or -X f5 -X 54 -(CH2) t5 - [In the formula, X f5 , X 53 , X 54 , s5 and t5 have the same meanings as above.] is.

[0244] More preferably, the above X A are each independently single bond, -X f5 -C 1-20 an alkylene group, -X f5 -(CH2) s5 -X 53 -(CH2)t5 -,or -X f5 -X 54 -(CH2) t5 - [In the formula, each symbol has the same meaning as above.] It could be.

[0245] In a preferred embodiment, the X A are each independently Single bond -X f5 -C 1-20 an alkylene group, -X f5 -(CH2) s5 -X 53 -,or -X f5 -(CH2) s5 -X 53 -(CH2) t5 - [In the formula, X 53 -O-, -CONR 54 -, or -O-CONR 54 - and R 54 are each independently in each occurrence a hydrogen atom, a phenyl group or C 1-6 represents an alkyl group, s5 is an integer from 1 to 20, t5 is an integer from 1 to 20. It could be.

[0246] In one embodiment, the X A are each independently single bond, -X f5 -C 1-20 an alkylene group, -X f5 -(CH2) s5 -O-(CH2) t5 -, -X f5 -(CH2) s5 -(Si(R 53 )2O) m5 -Si(R 53 )2-(CH2)t5 -, -X f5 -(CH2) s5 -O-(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2-(CH2) t5 -,or -X f5 -(CH2) s5 -O-(CH2) t5 -Si(R 53 )2-(CH2) u5 -Si(R 53 )2-(C v H 2v )- [In the formula, X f5 , R 53 , m5, s5, t5 and u5 are as defined above, and v5 is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3.] is.

[0247] In the above formula, -(C v H 2v )- can be straight or branched chain, for example, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)-, or -CH(CH3)CH2-.

[0248] Above X A are each independently a fluorine atom, C 1-3 Alkyl groups and C 1-3 Fluoroalkyl groups (preferably C 1-3 In one embodiment, X may be substituted with one or more substituents selected from the group consisting of: A is non-substituted.

[0249] Furthermore, the above X A The left side of each equation is R F1 or R F2 and the right side is R Si Combine with.

[0250] In one embodiment, X Aare each independently -OC 1-6 It may be other than an alkylene group.

[0251] In another embodiment, X A Examples of the group include the following: [ka] [ka] [In the formula, R 41 are each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or C 1-6 an alkoxy group, preferably a methyl group; D is -CH2O(CH2)2-, -CH2O(CH2)3-, -CF2O(CH2)3-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -CONH-(CH2)3-, -CON(CH3)-(CH2)3-, -CON(Ph)-(CH2)3- (wherein Ph means phenyl), and [ka] (In the formula, R 42 are each independently a hydrogen atom, C 1-6 alkyl group or C 1-6 represents an alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group. is a group selected from E is -(CH2) n - (n is an integer from 2 to 6), D is the R of the molecular main chain F1 or R F2 E is bonded to R Si Binds to.]

[0252] Above X ASpecific examples include, for example: single bond, -CH2OCH2-, -CH2O(CH2)2-, -CH2O(CH2)3-, -CH2O(CH2)6-, -CF2-CH2-O-CH2-, -CF2-CH2-O-(CH2)2-, -CF2-CH2-O-(CH2)3-, -CF2-CH2-O-(CH2)6-, -CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-, -CH2OCF2CHFOCF2-, -CH2OCF2CHFOCF2CF2-, -CH2OCF2CHFOCF2CF2CF2-, -CH2OCH2CF2CF2OCF2-, -CH2OCH2CF2CF2OCF2CF2-, -CH2OCH2CF2CF2OCF2CF2CF2-, -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-, -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-, -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-, <h2 style=";text-align:left;direction:ltr">-CH2OCH2CHFCF2OCF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CHFCF2OCF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CHFCF2OCF2CF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -(CH2)2-Si(CH3)2-(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CH2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -(CH2)3-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -(CH2)4-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -(CH2)5-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -(CH2)6-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CF2-CH2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CF2-(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CF2-(CH2)3-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CF2-(CH2)4-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CF2-(CH2)5-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CF2-(CH2)6-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CO-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CONH-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -CONH-CH2-、<h2 style=";text-align:left;direction:ltr"> -CONH-(CH2)2-, -CONH-(CH2)3-, -CONH-(CH2)6-, -CF2CONHCH2-, -CF2CONH(CH2)2-, -CF2CONH(CH2)3-, -CF2CONH(CH2)6-, -CON(CH3)-(CH2)3-, -CON(Ph)-(CH2)3- (wherein Ph means phenyl), -CON(CH3)-(CH2)6-, -CON(Ph)-(CH2)6- (wherein Ph means phenyl), -CF2-CON(CH3)-(CH2)3-, -CF2-CON(Ph)-(CH2)3- (wherein Ph means phenyl), -CF2-CON(CH3)-(CH2)6-, -CF2-CON(Ph)-(CH2)6- (wherein Ph means phenyl), -CONH-(CH2)2NH(CH2)3-, -CONH-(CH2)6NH(CH2)3-, -CH2O-CONH-(CH2)3-, -CH2O-CONH-(CH2)6-, -S-(CH2)3-, -(CH2)2S(CH2)3-, -CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-, -CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-, -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-, -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-, -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 10Si(CH3)2(CH2)2-, -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-, -C(O)O-(CH2)3-, -C(O)O-(CH2)6-, -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-, -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-, -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-, -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-, -OCH2-, -O(CH2)3-, -OCFHCF2-, [ka] Examples include:

[0253] In yet another embodiment, X A are each independently a group of the formula: -(R 16 ) x1 -(CFR 17 ) y1 -(CH2) z1 In the formula, x1, y1, and z1 each independently represent an integer of 0 to 10, the sum of x1, y1, and z1 is 1 or more, and the order of the repeating units enclosed in parentheses in the formula is arbitrary.

[0254] In the above formula, R 16 each occurrence independently represents an oxygen atom, phenylene, carbazolylene, -NR 18 -(In the formula, R 18 represents a hydrogen atom or an organic group) or a divalent organic group. 18is an oxygen atom or a divalent polar group.

[0255] The "divalent polar group" is not particularly limited, but examples thereof include -C(O)-, -C(=NR 19 )-, and -C(O)NR 19 -(wherein R 19 represents a hydrogen atom or a lower alkyl group). The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, or n-propyl, which may be substituted with one or more fluorine atoms.

[0256] In the above formula, R 17 are each independently a hydrogen atom, a fluorine atom, or a lower fluoroalkyl group, preferably a fluorine atom, in each occurrence. The "lower fluoroalkyl group" is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.

[0257] In yet another embodiment, X A Examples of include the following groups: [ka] [In the formula, R 41 are each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or C 1-6 The alkoxy group is preferably a methyl group; each X 101 In the group, any number of T's may be R's in the molecular main chain. F1 or R F2 The following groups are attached to: -CH2O(CH2)2-, -CH2O(CH2)3-, -CF2O(CH2)3-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -CONH-(CH2)3-, -CON(CH3)-(CH2)3-, -CON(Ph)-(CH2)3- (wherein Ph means phenyl), or [ka] [In the formula, R 42 are each independently a hydrogen atom, C 1-6 alkyl group or C 1-6 represents an alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group.] and some of the other Ts are Rs in the molecular backbone. Si and if present, the remaining Ts are each independently a methyl group, a phenyl group, or a C 1-6 It is an alkoxy group, a radical scavenger group, or an ultraviolet absorbing group.

[0258] The radical scavenging group is not particularly limited as long as it can capture radicals generated by light irradiation, and examples thereof include residues of benzophenones, benzotriazoles, benzoic acid esters, phenyl salicylates, crotonic acids, malonic acid esters, organoacrylates, hindered amines, hindered phenols, and triazines.

[0259] The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet light, and examples thereof include residues of benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, oxanilides, benzoxazinones, and benzoxazoles.

[0260] In a preferred embodiment, preferred radical scavenging groups or ultraviolet absorbing groups include: [ka] Examples include:

[0261] In this embodiment, X A may each independently be a trivalent to decavalent organic group.

[0262] In yet another embodiment, X A Examples of include the following groups: [ka] [In the formula, R 25 , R 26 and R 27 are each independently a divalent to hexavalent organic group, R 25 is at least one R F1 Binds to R 26 and R 27 Each has at least one R Si Binds to.]

[0263] In one embodiment, the R 25 is a single bond, C 1-20 Alkylene group, C 3-20 Cycloalkylene group, C 5-20 Arylene group, -R 57 -X 58 -R 59 -, -X 58 -R 59 -, or -R 57 -X 58 -. Above, R 57 and R 59 are each independently a single bond, C 1-20 Alkylene group, C 3-20 Cycloalkylene group, or C 5-20 The above X is an arylene group. 58 is -O-, -S-, -CO-, -O-CO- or -COO-.

[0264] In one embodiment, the R 26 and R 27 are each independently a hydrocarbon or a group having at least one atom selected from N, O and S at the end or in the main chain of the hydrocarbon, and preferably C 1-6Alkyl group, -R 36 -R 37 -R 36 -, -R 36 -CHR 38 2-, etc. Here, R 36 are each independently a single bond or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. 37 is N, O or S, preferably N or O. 38 -R 45 -R 46 -R 45 -, -R 46 -R 45 -or-R 45 -R 46 -. Here, R 45 are each independently an alkyl group having 1 to 6 carbon atoms. 46 is N, O or S, preferably O.

[0265] In this embodiment, X A may each independently be a trivalent to decavalent organic group.

[0266] The fluoropolyether group-containing compound represented by the above formula (1) or (2) is not particularly limited, but may be 5×10 2 ~1×10 5 Within this range, it is preferable from the viewpoint of friction durability that the average molecular weight is 2,000 to 32,000, more preferably 2,500 to 12,000. Note that the "average molecular weight" refers to a number average molecular weight, and the "average molecular weight" is 19 The value is measured by F-NMR.

[0267] In one embodiment, the fluorine-containing silane compound in the surface treatment agent used in the present disclosure is a compound represented by formula (1).

[0268] In another embodiment, the fluorine-containing silane compound in the surface treatment agent used in the present disclosure is a compound represented by formula (2).

[0269] In another embodiment, the fluorine-containing silane compound in the surface treatment agent used in the present disclosure is a compound represented by formula (1) and a compound represented by formula (2).

[0270] In the surface treatment agent used in the present disclosure, the compound represented by formula (2) preferably accounts for 0.1 mol% or more and 35 mol% or less of the total of the compound represented by formula (1) and the compound represented by formula (2). The lower limit of the content of the compound represented by formula (2) relative to the total of the compound represented by formula (1) and the compound represented by formula (2) is preferably 0.1 mol%, more preferably 0.2 mol%, even more preferably 0.5 mol%, even more preferably 1 mol%, particularly preferably 2 mol%, and especially 5 mol%. The upper limit of the content of the compound represented by formula (2) relative to the total of the compound represented by formula (1) and the compound represented by formula (2) is preferably 35 mol%, more preferably 30 mol%, even more preferably 20 mol%, even more preferably 15 mol% or 10 mol%. The compound represented by formula (2) is preferably 0.1 mol% or more and 30 mol% or less, more preferably 0.1 mol% or more and 20 mol% or less, even more preferably 0.2 mol% or more and 10 mol% or less, still more preferably 0.5 mol% or more and 10 mol% or less, particularly preferably 1 mol% or more and 10 mol% or less, for example, 2 mol% or more and 10 mol% or less, or 5 mol% or more and 10 mol% or less. By setting the compound represented by formula (2) in this range, friction durability can be further improved.

[0271] The compounds represented by the above formula (1) or (2) can be obtained, for example, by the methods described in Patent Document 1, Patent Document 2, and the like.

[0272] The surface treatment agent used in the present disclosure may include a solvent, a (non-reactive) fluoropolyether compound that can be understood as a fluorine-containing oil, preferably a perfluoro(poly)ether compound (hereinafter collectively referred to as a "fluorine-containing oil"), a (non-reactive) silicone compound that can be understood as a silicone oil (hereinafter referred to as a "silicone oil"), a catalyst, a surfactant, a polymerization inhibitor, a sensitizer, etc.

[0273] Examples of the solvent include aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate, and ethyl 2-hydroxybutyrate. Esters such as ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl amino ketone, 2-heptanone; ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether ... Glycol ethers such as ethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, and ethylene glycol monoalkyl ether; alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octyl alcohol, 3-methyl-3-methoxybutanol, and tert-amyl alcohol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, and diethylene glycol monomethyl ether; and diethylene glycol monoethyl ether acetate.Examples of the solvent include fluorine-containing solvents such as 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, dimethyl sulfoxide, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225), Zeorora H, HFE7100, HFE7200, and HFE7300. Alternatively, examples include mixed solvents of two or more of these solvents.

[0274] The fluorine-containing oil is not particularly limited, but examples thereof include compounds represented by the following general formula (3) (perfluoro(poly)ether compounds). Rf 5 -(OC4F8) a’ -(OC3F6) b’ -(OC2F4) c’ -(OCF2) d’ -Rf 6 ···(3) In the formula, Rf 5 is an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms (preferably, C 1―16 Rf represents a perfluoroalkyl group 6 is an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms (preferably, C 1-16 perfluoroalkyl group), a fluorine atom or a hydrogen atom, and Rf 5 and Rf 6 More preferably, each independently represents C 1-3 It is a perfluoroalkyl group. a', b', c', and d' respectively represent the number of four types of repeating units of the perfluoro(poly)ether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 300, and the sum of a', b', c', and d' is at least 1, preferably 1 to 300, and more preferably 20 to 300. The order of occurrence of each repeating unit enclosed in parentheses with the subscript a', b', c', or d' is arbitrary in the formula. Of these repeating units, -(OC4F8)- may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and (OCF2CF(C2F5))-, but is preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and (OCF2CF(CF3))-, but is preferably -(OCF2CF2CF2)-. -(OC2F4)- may be either -(OCF2CF2)- or (OCF(CF3))-, but is preferably -(OCF2CF2)-.

[0275] Examples of the perfluoro(poly)ether compound represented by the above general formula (3) include compounds represented by either of the following general formulas (3a) and (3b) (which may be one type or a mixture of two or more types): Rf 5 -(OCF2CF2CF2) b” -Rf 6 (3a) Rf 5 -(OCF2CF2CF2CF2) a” -(OCF2CF2CF2) b” -(OCF2CF2) c” -(OCF2) d” -Rf 6 (3b) In these formulas, Rf 5 and Rf 6is as defined above; in formula (3a), b" is an integer of 1 or more and 100 or less; in formula (3b), a" and b" are each independently an integer of 0 or more and 30 or less, and c" and d" are each independently an integer of 1 or more and 300 or less. The order of occurrence of each repeating unit enclosed in parentheses with the subscripts a", b", c", and d" is arbitrary in the formula.

[0276] From another perspective, fluorine-containing oils are those represented by the general formula Rf 3 -F(where Rf 3 is C 5-16 It may be a compound represented by the formula: wherein R is a perfluoroalkyl group.) It may also be a chlorotrifluoroethylene oligomer.

[0277] The fluorine-containing oil may have an average molecular weight of 500 to 10000. The molecular weight of the fluorine-containing oil can be measured using GPC.

[0278] The fluorinated oil may be contained in an amount of, for example, 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass, relative to the surface treatment agent. In one embodiment, the surface treatment agent is substantially free of fluorinated oil. "Substantially free of fluorinated oil" means that the surface treatment agent does not contain any fluorinated oil, or may contain a very small amount of fluorinated oil.

[0279] In one embodiment, the average molecular weight of the fluorine-containing oil may be larger than the average molecular weight of the fluorine-containing silane compound. By setting the average molecular weight in this manner, better friction durability and surface slipperiness can be obtained, particularly when the surface treatment layer is formed by vacuum deposition.

[0280] In one embodiment, the average molecular weight of the fluorine-containing oil may be smaller than the average molecular weight of the fluorine-containing silane compound. By setting the average molecular weight in this range, it is possible to form a cured product having high friction durability and high surface slippage while suppressing a decrease in the transparency of the surface treatment layer obtained from such a compound.

[0281] The fluorine-containing oil contributes to improving the surface slip properties of the layer formed by the surface treatment agent.

[0282] The silicone oil may be, for example, a linear or cyclic silicone oil having 2,000 or less siloxane bonds. The linear silicone oil may be a so-called straight silicone oil or a modified silicone oil. Examples of straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil. Examples of modified silicone oils include straight silicone oils modified with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, etc. Examples of cyclic silicone oils include cyclic dimethylsiloxane oil.

[0283] In the surface treatment agent, the silicone oil may be contained in an amount of, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass, relative to a total of 100 parts by mass of the fluorine-containing silane compounds (the total of these if two or more types are used, and the same applies below).

[0284] The silicone oil contributes to improving the surface slipperiness of the surface treatment layer.

[0285] Examples of the catalyst include acids (for example, acetic acid, trifluoroacetic acid, etc.), bases (for example, ammonia, triethylamine, diethylamine, etc.), and transition metals (for example, Ti, Ni, Sn, etc.).

[0286] The catalyst promotes the hydrolysis and dehydration condensation of the fluorine-containing silane compound, and promotes the formation of the layer formed by the surface treatment agent.

[0287] In addition to the above, other components include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and methyltriacetoxysilane.

[0288] The surface treatment agent used in the present disclosure can be impregnated into a porous substance, such as a porous ceramic material or a metal fiber, such as a flocculated steel wool, to form pellets, which can be used, for example, for vacuum deposition.

[0289] The thickness of the surface treatment layer is not particularly limited. In the case of optical members, the thickness of the layer is preferably in the range of 1 to 50 nm, 1 to 30 nm, and preferably 1 to 15 nm, from the viewpoints of optical performance, surface smoothness, friction durability, and antifouling properties.

[0290] The surface treatment layer can be formed, for example, by forming a layer of the surface treatment agent on the intermediate layer and then subjecting this layer to post-treatment as necessary.

[0291] The layer of the surface treatment agent can be formed by applying the surface treatment agent to the surface of the intermediate layer so as to coat the surface. The coating method is not particularly limited. For example, a wet coating method or a dry coating method can be used.

[0292] Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar methods.

[0293] Examples of dry coating methods include vapor deposition (usually vacuum deposition), sputtering, CVD, and similar methods. Specific examples of vapor deposition methods (usually vacuum deposition) include resistance heating, electron beam, high frequency heating using microwaves, ion beam, and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.

[0294] Furthermore, coating by atmospheric pressure plasma method is also possible.

[0295] When using the wet coating method, the surface treatment agent may be diluted with a solvent and then applied to the intermediate layer. From the viewpoint of the stability of the surface treatment agent and the volatility of the solvent, the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (e.g., bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., CF 13 CH2CH3 (e.g., Asahiklin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., Zeorora (registered trademark) H manufactured by Zeon Corporation); hydrofluoroethers (HFEs) (e.g., perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec (trademark) 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec (trademark) 7100 manufactured by Sumitomo 3M Limited), and alkyl perfluoroalkyl ethers (the perfluoroalkyl group and alkyl group may be linear or branched), such as perfluorobutyl ethyl ether (C4F9OC2H5) (e.g., Novec™ 7200 manufactured by Sumitomo 3M Limited) and perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (e.g., Novec™ 7300 manufactured by Sumitomo 3M Limited), or CF3CH2OCF2CHF2 (e.g., Asahiklin™ AE-3000 manufactured by Asahi Glass Co., Ltd.). These solvents can be used alone or as a mixture of two or more. Among these, hydrofluoroethers are preferred, with perfluorobutyl methyl ether (C4F9OCH3) and / or perfluorobutyl ethyl ether (C4F9OC2H5) being particularly preferred.

[0296] When the dry coating method is used, the surface treatment agent may be subjected to the dry coating method as it is, or may be diluted with the above-mentioned solvent before being subjected to the dry coating method.

[0297] The layer formation of the surface treatment agent is preferably carried out so that the surface treatment agent is present in the layer together with a catalyst for hydrolysis and dehydration condensation. Conveniently, in the case of a wet coating method, the surface treatment agent may be diluted with a solvent, and then a catalyst may be added to the diluted solution of the surface treatment agent immediately before application to the surface of the intermediate layer. In the case of a dry coating method, the surface treatment agent to which the catalyst has been added may be directly vapor-deposited (usually vacuum vapor-deposited), or a pellet-shaped material impregnated with the surface treatment agent to which the catalyst has been added may be vapor-deposited (usually vacuum vapor-deposited) onto a porous metal such as iron or copper.

[0298] Any suitable acid or base can be used as the catalyst. Examples of acid catalysts that can be used include acetic acid, formic acid, and trifluoroacetic acid. Examples of base catalysts that can be used include ammonia and organic amines.

[0299] As described above, a layer derived from the surface treatment agent is formed on the surface of the intermediate layer, and the article of the present disclosure is manufactured. The surface treatment layer obtained thereby has high friction durability. In addition to high friction durability, depending on the composition of the surface treatment agent used, the layer may have water repellency, oil repellency, antifouling properties (for example, preventing adhesion of stains such as fingerprints), waterproof properties (preventing water penetration into electronic components, etc.), surface slipperiness (or lubricity, for example, ease of wiping off stains such as fingerprints and excellent tactile feel), etc., and can be suitably used as a functional thin film.

[0300] The article of the present disclosure may further be an optical material having the above-described surface treatment layer as the outermost layer.

[0301] The article of the present disclosure may be, but is not particularly limited to, an optical member. Examples of optical members include lenses for eyeglasses and the like; front protective plates, anti-reflection plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and personal digital assistants; disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; optical fibers; and the display surfaces of watches and clocks.

[0302] The article of the present disclosure may also be a medical device or medical material.

[0303] The article of the present disclosure has high chemical resistance and high friction durability by having, on a substrate, an intermediate layer containing a Si-containing composite oxide and, on the intermediate layer, a surface treatment layer formed from a surface treatment agent containing a fluorine-containing silane compound.

[0304] The article of the present disclosure can be obtained by forming an intermediate layer containing a Si-containing composite oxide on a substrate, and then forming a surface treatment layer thereon from a surface treatment agent containing a fluorine-containing silane compound.

[0305] Typically, the articles of the present disclosure can be produced by simultaneously depositing Si and other atoms onto a substrate.

[0306] Accordingly, the present disclosure further provides: A method for producing an article having a substrate and a surface treatment layer formed thereon from a surface treatment agent containing a fluorine-containing silane compound, comprising: On the substrate, Si and another metal are simultaneously vapor-deposited to form an intermediate layer containing a composite oxide containing Si; forming a surface treatment layer directly on the intermediate layer; The present invention provides a method comprising:

[0307] The articles of the present disclosure may be fabricated by sequentially depositing Si and other atoms onto a substrate.

[0308] The article of the present disclosure has been described in detail above. However, the article and the method for manufacturing the article of the present disclosure are not limited to the examples given above. [Example]

[0309] The articles of the present disclosure will be described below in examples, but the present disclosure is not limited to the following examples. Note that in these examples, the chemical formulas shown below all represent average compositions, and the repeating units constituting the fluoropolyether ((CFCFCFO), (CF(CF)CFO), (CFCFO), (CFO), etc.) may be present in any order.

[0310] The glass substrate was made of Gorilla Glass 3 (manufactured by Corning Incorporated), which was 0.5 mm thick, 71.5 mm x 149.0 mm, and had been chemically strengthened and surface polished. After forming an intermediate layer, a surface treatment layer was formed on the intermediate layer to obtain a glass substrate with a surface treatment layer. The details are as follows.

[0311] (Formation of intermediate layer) The intermediate layer was formed by placing a silicon target and a tantalum or niobium target in a RAS or DC sputtering device, introducing a mixed gas of argon and oxygen into the chamber, and depositing an intermediate layer made of a composite oxide of silicon and tantalum or niobium to a thickness of 10 to 40 nm at various deposition rate ratios (Si / Ta) while setting sputtering conditions for each example.

[0312] The formation of the surface treatment layer is carried out using a device that can carry out resistance heating deposition.Specifically, the composition containing the fluorine-containing organosilicon compound is introduced into a heating container, and then the container is evacuated with a vacuum pump, and the solvent is distilled off, and then the heating container is heated, thereby forming the surface treatment layer on the intermediate layer.The fluorine-containing organosilicon compound used is a compound having the following structure.

[0313] Compound A CF3O(CF2CF2O) 15 (CF2O) 16 CF2CH2OCH2CH2CH2Si[CH2CH2CH2Si(OCH3)3]3 Compound B CF3CF2CF2O(CF2CF2CF2O) 25 CF2CF2(CH2CH[Si(OCH3)3])3H Compound C CF3CF2CF2O(CF2CF2CF2O) 23 CF2CF2CONHCH2CH2CH2Si(OCH3)3 Compound D CF3CF2CF2O(CF2CF2CF2O) 23 CF2CF2CONHCH2C[CH2CH2CH2Si(OCH3)3]3 Compound E [(CH3O)3SiCH2CH2CH2]3CCH2NHCOCF2O(CF2CF2O) 10 (CF2O) 10 CF2CONHCH2C[CH2CH2CH2Si(OCH3)3]3 Compound F [(CH3O)3SiCH2CH2CH2]3CCH2NHCOCF2O(CF2CF2O)8(CF2O) 14 CF2CONHCH2C[CH2CH2CH2Si(OCH3)3]3 Compound G [(CH3O)3SiCH2CH2CH2]3CCH2NHCOCF2CF2O(CF2CF2CF2O) 16 CF2CF2CONHCH2C[CH2CH2CH2Si(OCH3)3]3 Compound H CF3CF2CF2O[CF(CF3)CF2O] 22 CFCONHCH2C[CH2CH2CH2Si(OCH3)3]3

[0314] [Table 1]

[0315] <Evaluation> The glass substrates with the surface treatment layers obtained above were subjected to measurement of water contact angle, alkali test, and evaluation of friction durability as follows.

[0316] (Alkaline immersion test) A 1-cm diameter PTFE O-ring was placed on the surface of the substrate treated in Examples 3, 4, 7, 10-13, and 17, and Comparative Examples 1, 4-6, and 10. An 8N NaOH solution (alkaline aqueous solution) was dropped into the O-ring, bringing the surface of the surface-treated layer into contact with the alkaline aqueous solution, and subjected to an alkaline immersion test. After 20 to 360 minutes of alkaline immersion, the alkaline aqueous solution was wiped off, the glass substrate was washed with pure water and ethanol, and the contact angle with water was measured. The static contact angle with water was measured by placing a 2-μL droplet of pure water on the surface of the glass substrate after the alkaline immersion test using a contact angle meter (DropMaster 701, Kyowa Interface Science Co., Ltd.). The static contact angle with water was measured at five locations after the alkaline immersion test. If the measured static contact angle with water decreased within 360 minutes, the alkaline immersion test was stopped. The relationship between the immersion time and the average value of the contact angles at five locations is shown in Table 2 below.

[0317] [Table 2]

[0318] (Abrasion durability test) A sample article with a surface treatment layer formed was placed horizontally, and the friction element described below was placed in contact with the surface of the surface treatment layer (contact surface: a circle with a diameter of 1 cm). A load of 5 N was applied to the friction element. Then, with the load applied, the friction element was moved back and forth at a speed of 40 mm / s. The friction element was moved back and forth up to 3,000 times for Examples 1 and 2 and Comparative Example 1, and up to 10,000 times for Examples 3 to 6, 8 to 9, and 11 to 17 and Comparative Examples 2 to 10. The static contact angle of water (°) was measured every 500 or 1,000 times. The test was stopped when the measured static contact angle of water fell below 60°. The static contact angle of water was measured in the same manner as in the alkali test described above. The results are shown in Table 3 below for Examples 1 and 2 and Comparative Example 1 using RAS, Table 4 below for Examples 3 to 6, 8 to 9, and 11 to 17 using DC, and Table 5 below for Comparative Examples 2 to 10.

[0319] ·Friction element The surface of the silicone rubber processed product shown below (1 cm in diameter) was covered with cotton soaked in artificial sweat of the composition shown below and used as a friction element. Artificial sweat composition: Anhydrous disodium hydrogen phosphate: 2g Sodium chloride: 20g 85% lactic acid: 2g Histidine hydrochloride: 5g Distilled water: 1 kg Silicone rubber processed products: The silicone rubber stopper SR-51 manufactured by Tigers Polymer is processed into a cylindrical shape with a diameter of 1 cm and a thickness of 1 cm.

[0320] [Table 3]

[0321] [Table 4]

[0322] [Table 5]

[0323] (Surface analysis) The composition (depth direction analysis) of the treated surface of the above-mentioned treated glass substrate was analyzed using an X-ray photoelectron spectrometer (XPS, PHI5000VersaProbeII manufactured by ULVAC-PHI, Inc.) The measurement conditions for XPS analysis were as follows: X-ray source: Monochromated AlKα radiation (25W) Photoelectron detection area: 1400 μm x 300 μm Photoelectron detection angle: 20 degrees, 45 degrees, 90 degrees Pass energy: 23.5 eV

[0324] For the glass substrates with surface-treated layers in Examples 1 and 2, the peak areas of C1s, O1s, F1s, Si2p, and Ta4f orbitals were observed by the above-mentioned XPS, and the atomic ratios and area ratios of carbon, oxygen, fluorine, silicon, and tantalum were calculated to determine the composition of the treated surface including the surface-treated antifouling layer. The results for Examples 1 and 2 using RAS are shown in Table 6 below.

[0325] [Table 6]

[0326] (Surface analysis) The composition (depth direction analysis) of the treated surface of the above-mentioned treated glass substrate was analyzed using an X-ray photoelectron spectrometer (XPS, PHI5000VersaProbeII manufactured by ULVAC-PHI, Inc.) The measurement conditions for XPS analysis were as follows: X-ray source: Monochromated AlKα radiation (25W) Photoelectron detection area: 1400 μm x 300 μm Photoelectron detection angle: 45 degrees Pass energy: 23.5 eV Sputter ions: Ar ions

[0327] The glass substrates with surface-treated layers in Examples 1 to 7 were sputtered with Ar ions for a predetermined time to gradually etch the layers on the substrate (surface-treated layer and intermediate layer) in the depth direction. After each predetermined time, the peak areas of the O1s, Si2p, and Ta4f orbitals were observed using the XPS described above, and the atomic and area ratios of oxygen and silicon were calculated to determine the composition of the layer on the substrate surface. The etching rate during sputtering was 3 nm / min. The results for Examples 1 to 7 are shown in Table 7 below.

[0328] [Table 7]

[0329] From the above analysis results, it was confirmed that the examples in which the Si / Ta ratio was 0.15 to 12.0 (Si:Ta=13:87 to 93:7) had high alkali resistance and friction durability.

[0330] As can be seen from the above results, Examples 1 to 17, in which an intermediate layer consisting of Si, Ta, and O or an intermediate layer consisting of Si, Nb, and O was formed between the substrate and the surface treatment layer, showed a suppressed decrease in contact angle in the alkali immersion test and were confirmed to have excellent alkali durability, compared to Comparative Examples 1 to 10, which did not have such an intermediate layer. Furthermore, Examples 1 to 4 showed a suppressed decrease in contact angle in the abrasion durability test and were confirmed to have excellent abrasion durability using artificial sweat. [Industrial Applicability]

[0331] The articles of the present disclosure can be suitably used in a wide variety of applications, for example, as optical components.

Claims

1. A substrate; an intermediate layer positioned on the substrate; a surface treatment layer formed from a surface treatment agent containing a fluorine-containing silane compound and positioned directly on the intermediate layer; and the intermediate layer contains a composite oxide containing Si, the composite oxide is a composite oxide of Si and another metal, and the molar ratio of Si to the other metal is 13:87 to 93:7; the other metal is Ta or Nb, The composite oxide is a homogeneous phase of Si and an oxide of another metal. Goods.

2. 2. The article according to claim 1, wherein the molar ratio of Si to the other metal in the composite oxide is 45:55 to 75:

25.

3. The fluorine-containing silane compound is represented by the following formula (1) or (2): 【Chemical 1】 [In the formula: R Ｆ１ is independently at each occurrence Rf １ -R Ｆ -O ｑ - and; R Ｆ２ is -Rf ２ ｐ -R Ｆ -O ｑ - and; Rf １ each occurrence independently represents a C optionally substituted by one or more fluorine atoms; １－１６ is an alkyl group; Rf ２ is a C optionally substituted by one or more fluorine atoms; １－６ an alkylene group; R Ｆ is independently in each occurrence a divalent fluoropolyether group; p is 0 or 1; q is independently in each occurrence 0 or 1; R Ｓｉ is independently in each occurrence a monovalent group containing a Si atom to which is bonded a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group; At least one R Ｓｉ is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded; X Ａ are each independently a single bond or a divalent to decavalent organic group; α is an integer from 1 to 9; β is an integer from 1 to 9; Each γ is independently an integer from 1 to 9.

3. The article according to claim 1, wherein the compound is at least one fluoropolyether group-containing compound represented by the formula:

4. Rf １ independently in each occurrence, C １－１６ is a perfluoroalkyl group, Rf ２ independently in each occurrence, C １－６ is a perfluoroalkylene group, The article of claim 3.

5. R Ｆ independently in each occurrence represents the formula: -(OC ６ F １２ ) ａ -(OC ５ F １０ ) ｂ -(OC ４ F ８ ) ｃ -(OC ３ R Ｆａ ６ ) ｄ -(OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - [In the formula, R Ｆａ is independently in each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom; a, b, c, d, e, and f each independently represent an integer of 0 to 200, the sum of a, b, c, d, e, and f is 1 or more, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] The article according to claim 3 or 4, wherein the group is represented by:

6. R Ｆａ The article of claim 5 , wherein is a fluorine atom.

7. R Ｆ is independently in each occurrence a group represented by the following formula (f1), (f2) or (f3): -(OC ３ F ６ ) ｄ - (f1) [In the formula, d is an integer of 1 to 200.] -(OC ４ F ８ ) ｃ -(OC ３ F ６ ) ｄ -(OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - (f2) wherein c and d each independently represent an integer of 0 to 30; e and f are each independently an integer from 1 to 200; the sum of c, d, e and f is an integer from 10 to 200; The order of occurrence of each repeating unit enclosed in parentheses with the subscript c, d, e, or f is arbitrary in the formula.] -(R ６ -R ７ ) ｇ - (f3) [In the formula, R ６ is OCF ２ or O.C. ２ F ４ and R ７ is O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups selected from these groups; g is an integer from 2 to 100. The article according to any one of claims 3 to 6, wherein the group is represented by:

8. R Ｓｉ is represented by the following formula (S1), (S2), (S3), or (S4): 【Chemistry 2】 [In the formula: R １１ is independently in each occurrence a hydroxyl group or a hydrolyzable group; R １２ is independently in each occurrence a hydrogen atom or a monovalent organic group; n1 is (SiR １１ ｎ１ R １２ ３－ｎ１ ) units are each independently an integer from 0 to 3; X １１ is independently in each occurrence a single bond or a divalent organic group; R １３ is independently in each occurrence a hydrogen atom or a monovalent organic group; t is independently in each occurrence an integer from 2 to 10; R １４ is independently in each occurrence a hydrogen atom or a halogen atom; R ａ１ is independently at each occurrence -Z １ -SiR ２１ ｐ１ R ２２ ｑ１ R ２３ ｒ１ and Z １ is independently in each occurrence an oxygen atom or a divalent organic group; R ２１ is independently at each occurrence -Z １’ -SiR ２１’ ｐ１’ R ２２’ ｑ１’ R ２３’ ｒ１’ and R ２２ is independently in each occurrence a hydroxyl group or a hydrolyzable group; R ２３ is independently in each occurrence a hydrogen atom or a monovalent organic group; p1, in each occurrence, is independently an integer from 0 to 3; q1 in each occurrence is independently an integer from 0 to 3; r1 in each occurrence is independently an integer from 0 to 3; Z １’ is independently in each occurrence an oxygen atom or a divalent organic group; R ２１’ is independently at each occurrence -Z １” -SiR ２２” ｑ１” R ２３” ｒ１” and R ２２’ is independently in each occurrence a hydroxyl group or a hydrolyzable group; R ２３’ is independently in each occurrence a hydrogen atom or a monovalent organic group; p1' in each occurrence is independently an integer from 0 to 3; q1' in each occurrence is independently an integer from 0 to 3; r1' in each occurrence is independently an integer from 0 to 3; Z １” is independently in each occurrence an oxygen atom or a divalent organic group; R ２２” is independently in each occurrence a hydroxyl group or a hydrolyzable group; R ２３” is independently in each occurrence a hydrogen atom or a monovalent organic group; q1″ in each occurrence is independently an integer from 0 to 3; r1″ in each occurrence is independently an integer from 0 to 3; R ｂ１ is independently in each occurrence a hydroxyl group or a hydrolyzable group; R ｃ１ is independently in each occurrence a hydrogen atom or a monovalent organic group; k1, in each occurrence, is independently an integer from 0 to 3; l1 in each occurrence is independently an integer from 0 to 3; m1 in each occurrence is independently an integer from 0 to 3; R ｄ１ is independently at each occurrence -Z ２ -CR ３１ ｐ２ R ３２ ｑ２ R ３３ ｒ２ and Z ２ is independently in each occurrence a single bond, an oxygen atom, or a divalent organic group; R ３１ is independently at each occurrence -Z ２’ -CR ３２’ ｑ２’ R ３３’ ｒ２’ and R ３２ is independently at each occurrence -Z ３ -SiR ３４ ｎ２ R ３５ ３－ｎ２ and R ３３ is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; p2 in each occurrence is independently an integer from 0 to 3; q2 in each occurrence is independently an integer from 0 to 3; r2 in each occurrence is independently an integer from 0 to 3; Z ２’ is independently in each occurrence a single bond, an oxygen atom, or a divalent organic group; R ３２’ is independently at each occurrence -Z ３ -SiR ３４ ｎ２ R ３５ ３－ｎ２ and R ３３’ is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; q2' in each occurrence is independently an integer from 0 to 3; r2' is independently in each occurrence an integer from 0 to 3; Z ３ is independently in each occurrence a single bond, an oxygen atom, or a divalent organic group; R ３４ is independently in each occurrence a hydroxyl group or a hydrolyzable group; R ３５ is independently in each occurrence a hydrogen atom or a monovalent organic group; n2 in each occurrence is independently an integer from 0 to 3; R ｅ１ is independently at each occurrence -Z ３ -SiR ３４ ｎ２ R ３５ ３－ｎ２ and R ｆ１ is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; k2 in each occurrence is independently an integer from 0 to 3; l2 in each occurrence is independently an integer from 0 to 3; m2 in each occurrence is independently an integer from 0 to 3. The article according to any one of claims 3 to 7, wherein the group is represented by:

9. The article of any one of claims 3 to 8, wherein α, β, and γ are 1.

10. X Ａ are each independently a trivalent organic group, α is 1 and β is 2, or α is 2 and β is 1, γ is 2, The article according to any one of claims 3 to 8.

11. The article according to any one of claims 1 to 10, wherein the substrate is a glass substrate.

12. The article according to any one of claims 1 to 11, wherein the intermediate layer has a thickness of 100 nm or less.

13. The article according to any one of claims 1 to 12, wherein the intermediate layer has a thickness of 50 nm or less.

14. A method for producing an article having a substrate and a surface treatment layer formed thereon from a surface treatment agent containing a fluorine-containing silane compound, comprising: forming an intermediate layer containing a composite oxide containing Si by simultaneously depositing Si and another metal on the substrate; and forming a surface treatment layer directly on the intermediate layer; Including, the intermediate layer contains a composite oxide containing Si, the composite oxide is a composite oxide of Si and another metal, and the molar ratio of Si to the other metal is 13:87 to 93:7; the other metal is Ta or Nb, The composite oxide is a homogeneous phase of Si and an oxide of another metal.

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