Articles and methods for manufacturing articles

Abstract

The present disclosure aims to provide an article having a surface treatment layer with good durability. 【Solution means】A substrate (A), a water and oil repellent layer (C), and a silicon oxide layer (B) disposed between the substrate (A) and the water and oil repellent layer (C) and containing one or more selected from the group consisting of an alkali metal atom and Cl , , NO3 - , SO3 - , SO4 2- , PO3 - and PO4 3- ; and an article, wherein the silicon oxide layer (B) has an average value of the concentration of alkali metal atoms in the region where the depth from the surface in contact with the water and oil repellent layer (C) is 0.1 to 0.3 nm of 1.4×10 atoms / cm 18 or more and less than 2.0×10 3 atoms / cm 19 and the water and oil repellent layer (C) is formed using a surface treatment agent containing a silane compound having a Si atom to which a hydroxyl group or a hydrolyzable group is bonded, 3 and the silane compound has a fluorine atom. The water and oil repellent layer (C) is formed using a surface treatment agent containing a silane compound having a Si atom to which a hydroxyl group or a hydrolyzable group is bonded. The silane compound has a fluorine atom.

Description

[Technical Field]

[0001] This disclosure relates to articles and methods for manufacturing articles. [Background technology]

[0002] Certain silane compounds are known to provide excellent water repellency, oil repellency, and stain resistance when used for surface treatment of substrates. Layers obtained from surface treatment agents 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, fibers, sanitary products, and building materials (Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2019-116097 [Patent Document 2] U.S. Patent Publication No. 2020 / 0333510 [Overview of the project] [Problems that the invention aims to solve]

[0004] There was room for improvement in the durability of the surface treatment layer formed from the above-mentioned silane compound.

[0005] This disclosure aims to provide articles having a surface treatment layer with good durability. [Means for solving the problem]

[0006] This disclosure includes the following: [1] Base material (A), Water-repellent and oil-repellent layer (C), Displaced between the substrate (A) and the water-repellent and oil-repellent layer (C), alkali metal atoms and Cl - NO3 - , SO3 - SO42- and PO3 - and PO4 3- and includes one or more selected from the group consisting of, a silicon oxide layer (B). In the region where the depth from the surface in contact with the water and oil repellent layer (C) of the silicon oxide layer (B) is 0.1 to 0.3 nm, the average value of the concentration of alkali metal atoms is 1.4 × 10 18 atoms / cm 3 or more and 2.0 × 10 19 atoms / cm 3 less than, The water and oil repellent layer (C) is formed using a surface treatment agent containing a silane compound having a Si atom to which a hydroxyl group or a hydrolyzable group is bonded, The silane compound has a fluorine atom, an article. [2] The article according to [1], wherein the alkali metal atom includes a sodium atom. [3] The silicon oxide layer (B) contains one or more selected from the group consisting of Cl - , SO3 - and NO3 - , the article according to [1] or [2]. [4] The silicon oxide layer (B) contains a sodium atom and one or more selected from the group consisting of Cl - , SO3 - and NO3 - , the article according to any one of [1] to [3]. [5] The silicon oxide layer (B) contains one or more selected from condensates of silicic acid compounds and hydrolyzates of alkoxysilanes, the article according to any one of [1] to [4]. [6] The silicon oxide layer (B) is formed from a binder composition, The binder composition contains a silicon oxide precursor, an acid, and an alkali metal salt, the article according to any one of [1] to [5]. [7] The silicon oxide layer (B) is formed from a liquid binder composition, The article according to any one of [1] to [6], wherein the liquid binder composition comprises a silicon dioxide precursor, an acid, an alkali metal salt, and a solvent. [8] The article according to [6], wherein the silicon dioxide precursor comprises one or more selected from silicic acid compounds, condensates of silicic acid compounds, alkoxysilanes, and hydrolysis condensates of alkoxysilanes. [9] The silane compound in the water-repellent and oil-repellent layer (C) is of the following formula (1) or (2): [ka] [In formula: R F1 Each of them is independent of Rf 1 -R F -O q -and; R F2 -Rf 2 p -R F -O q -and; Rf 1 Each of these C atoms may be independently substituted with one or more fluorine atoms. 1-16 It is an alkyl group; Rf 2 C may be substituted with one or more fluorine atoms. 1-6 It is an alkylene group; R F Each of these is independently a divalent fluoropolyether group; p is either 0 or 1; q is either 0 or 1, independently of each other; R Si Each of these is independently a monovalent group containing a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a Si atom to which a monovalent organic group is bonded; at least one R Si This is a monovalent group containing a Si atom to which a hydroxyl group or hydrolyzable group is bonded; X A Each of these is independently a single bond or a 2-10 valent organic group; α is an integer between 1 and 9; β is an integer between 1 and 9; Each of the γ values ​​is an independent integer between 1 and 9. The article according to any one of [1] to [8], comprising at least one silane compound represented by .

[10] The silane compound is, in formula (1) or (2) above, R Si However, the following equations (S1), (S2), (S3), (S4), or (S5): [ka] [In formula: R 11 Each of these is independently a hydroxyl group or a hydrolyzable group, R 12 Each of these is independently a monovalent organic group, n1 is (SiR 11 n1 R 12 3-n1 Each unit is an independent integer between 0 and 3. X 11 Each of these is independently a single bond or a divalent organic group. R 13 Each of these is independently a hydrogen atom or a monovalent organic group. Each t is an independent integer greater than or equal to 2. R 14 Each of these is independently a hydrogen atom, a halogen atom, or -X 11 -SiR 11 n1 R 12 3-n1 And, R 15 Each of these is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkylene oxy group having 1 to 6 carbon atoms. R a1 These are, independently, -Z 1 -SiR 21 p1 R 22 q1 R 23 r1and; Z 1 These are, independently, divalent organic groups, R 21 These are, independently, -Z 1’ -SiR 21’ p1’ R 22’ q1’ R 23’ r1’ and; R 22 Each of these is independently a hydroxyl group or a hydrolyzable group, R 23 Each of these is independently a monovalent organic group, p1 is an integer between 0 and 3, independently of each other. Each q1 is an integer between 0 and 3, independently of the others. Each r1 is an independent integer between 0 and 3. Z 1’ These are, independently, divalent organic groups, R 21’ These are, independently, -Z 1” -SiR 22” q1” R 23” r1” and; R 22’ Each of these is independently a hydroxyl group or a hydrolyzable group, R 23’ Each of these is independently a monovalent organic group, p1' are each independent integers between 0 and 3. Each of q1' is an independent integer between 0 and 3. r1' are each independent integers between 0 and 3. Z 1” These are, independently, divalent organic groups, R 22” Each of these is independently a hydroxyl group or a hydrolyzable group, R 23” Each of these is independently a monovalent organic group, Each of q1'' is an independent integer between 0 and 3. Each of r1'' is an independent integer between 0 and 3. R b1 is, independently of each other, a hydroxyl group or a hydrolyzable group, R c1 is, independently of each other, a monovalent organic group, k1 is, independently of each other, an integer from 0 to 3, l1 is, independently of each other, an integer from 0 to 3, m1 is, independently of each other, an integer from 0 to 3, However, in formula (S3), there are at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded, R d1 is, independently of each other, -Z 2 -CR 31 p2 R 32 q2 R 33 r2 and Z 2 is, independently of each other, a single bond, an oxygen atom or a divalent organic group, R 31 is, independently of each other, -Z 2’ -CR 32’ q2’ R 33’ r2’ and R 32 is, independently of each other, -Z 3 -SiR 34 n2 R 35 3-n2 and R 33 is, independently of each other, a hydrogen atom, a hydroxyl group or a monovalent organic group, p2 is, independently of each other, an integer from 0 to 3, q2 is, independently of each other, an integer from 0 to 3, r2 is, independently of each other, an integer from 0 to 3, Z 2’ is, independently of each other, a single bond, an oxygen atom or a divalent organic group, R 32’ is, independently of each other, -Z 3 -SiR 34 n2 R35 3-n2 And, R 33’ Each of these is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. q2' are each independent integers between 0 and 3. r2' are each independent integers between 0 and 3. Z 3 Each of these is independently a single bond, an oxygen atom, or a divalent organic group; R 34 Each of these is independently a hydroxyl group or a hydrolyzable group, R 35 Each of these is independently a monovalent organic group, n2 are each an independent integer between 0 and 3. R e1 These are, independently, -Z 3 -SiR 34 n2 R 35 3-n2 And, R f1 Each of these is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. k2 are each an independent integer between 0 and 3. l2 are each an independent integer between 0 and 3. Each of the m2 values ​​is an independent integer between 0 and 3. However, in formula (S4), there are at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded, R g1 and R h1 These are, independently, -Z 4 -SiR 11 n1 R 12 3-n1 , -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 , or -Z 4 -CR d1 k2 R e1 l2 Rf1 m2 And, Z 4 Each of these is independently a single bond, an oxygen atom, or a divalent organic group. However, in formula (S5), there are at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded. The article according to [9], comprising a compound which is a group represented by .

[11] A method for manufacturing an article, The aforementioned article comprises a base material (A) and A water- and oil-repellent layer (C) formed from a silane compound containing Si atoms to which hydroxyl groups or hydrolyzable groups are bonded, Displaced between the substrate (A) and the water-repellent and oil-repellent layer (C), alkali metal atoms and Cl - NO3 - , SO3 - SO4 2- , PO3 - and PO4 3- A silicon oxide layer (B) comprising one or more selected from the group consisting of the following, In the silicon oxide layer (B), in the region at a depth of 0.1 to 0.3 nm from the surface in contact with the water-repellent and oil-repellent layer (C), the average concentration of alkali metal atoms is 1.4 × 10⁻¹⁶. 18 atoms / cm 3 The above 2.0 × 10 19 atoms / cm 3 It is less than, The silane compound is a method for producing an article having a fluorine atom. [Effects of the Invention]

[0007] This disclosure may provide articles having a surface treatment layer with good durability. [Modes for carrying out the invention]

[0008] The articles disclosed herein are Base material (A), Water-repellent and oil-repellent layer (C), Displaced between the substrate (A) and the water-repellent and oil-repellent layer (C), alkali metal atoms and Cl- NO3 - , SO3 - SO4 2- , PO3 - and PO4 3- A silicon oxide layer (B) comprising one or more selected from the group consisting of, In the silicon oxide layer (B), in the region at a depth of 0.1 to 0.3 nm from the surface in contact with the water-repellent and oil-repellent layer (C), the average concentration of alkali metal atoms is 1.4 × 10⁻¹⁶. 18 atoms / cm 3 The above 2.0 × 10 19 atoms / cm 3 It is less than, The water- and oil-repellent layer (C) is formed using a surface treatment agent containing a silane compound having a Si atom to which a hydroxyl group or hydrolyzable group is bonded. The silane compound has a fluorine atom.

[0009] The articles of this disclosure exhibit good durability of the surface treatment layer. While this disclosure should not be construed as limiting to any particular theory, the reasons why the articles of this disclosure may exhibit such effects are thought to be as follows: When surface treatment is performed using a silane compound containing fluorine atoms, the adhesion between the surface treatment layer and the substrate can be improved by using a silicon oxide layer. Furthermore, it has become clear that the durability of the surface treatment layer can be improved by including alkali metal atoms in the silicon oxide layer. It is thought that the inclusion of alkali metal atoms in the silicon oxide layer increases the amount of silanol groups on the surface of the silicon oxide layer, increasing the number of reaction sites, which in turn improves the adhesion between the silicon oxide layer and the water- and oil-repellent layer, thereby improving durability.

[0010] Base material (A) The substrate (A) usable in this disclosure is not particularly limited. The substrate (A) may consist of any suitable material, such as glass, resin (natural or synthetic resin, for example, general plastic materials, preferably polycarbonate resin, poly(meth)acrylate resin, polyethylene terephthalate resin, triacetylcellulose resin, polyimide resin, modified (transparent) polyimide resin, polycycloolefin resin, polyethylene naphthalate resin, and may be in the form of a plate, film, or other), metal (may be a composite of a single metal or alloy such as aluminum, copper, silver, or iron), ceramics, semiconductor (silicon, germanium, etc.), fiber (textiles, nonwovens, etc.), fur, leather, wood, ceramics, stone, building materials, etc.

[0011] For example, if the article to be manufactured is an optical component, the material constituting the surface of the substrate (A) may be an optical component material, such as glass or transparent plastic. Furthermore, the substrate (A) may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coat layer, an anti-reflective layer, a polarizing film, a phase difference film, an organic EL display module, and a liquid crystal display module, depending on its specific specifications. Either a single-layer anti-reflective layer or a multi-layer anti-reflective layer may be used for the anti-reflective layer. Examples of inorganic materials that can be used for the anti-reflective 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 individually or in combination of two or more (for example, as a mixture). When a multi-layer anti-reflective layer is used, it is preferable to use SiO2 and / or SiO for the outermost layer. If the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode, such as indium tin oxide (ITO) or indium zinc oxide, may be present on a part 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, and a liquid crystal display module, depending on its specific specifications.

[0012] The shape of the substrate (A) is not particularly limited. Furthermore, the surface area of ​​the substrate on which the film (surface treatment layer) is to be formed only needs to be at least a part of the surface of the substrate (A), and can be appropriately determined according to the intended use and specific specifications of the article to be manufactured.

[0013] In one embodiment, the substrate may consist of a material that originally has hydroxyl groups, at least on its surface. Examples of such materials include glass, metals (especially base metals) on which a native oxide film or thermal oxide film is formed on the surface, ceramics, semiconductors, etc. Alternatively, if the material has insufficient hydroxyl groups, such as resins, or if it does not originally have hydroxyl groups, the substrate can be pretreated to introduce or increase hydroxyl groups on its surface. Examples of such pretreatment 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 suitably 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 formed in the form of a monolayer on the substrate surface by the LB method (Langmuir-Bludget method) or chemical adsorption method, and then the unsaturated bonds are cleaved in an atmosphere containing oxygen or nitrogen.

[0014] In another embodiment, such a substrate may consist of a material in which at least its surface portion is made of another reactive group, such as a silicone compound having one or more Si-H groups, or an alkoxysilane.

[0015] In a preferred embodiment, the substrate is glass. Preferred glass includes sapphire glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, quartz glass, and crystallized glass, with chemically strengthened soda-lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glass being particularly preferred.

[0016] Silicon oxide layer (B) The silicon oxide layer (B) is positioned between the substrate (A) and the water-repellent and oil-repellent layer (C), and is a layer mainly composed of silicon oxide, containing alkali metal atoms and Cl - , SO3 - NO3 - SO4 2- , PO3- and PO4 3- It includes one or more species selected from the group consisting of the following.

[0017] Examples of the alkali metal atoms mentioned above include lithium, sodium, and potassium, with sodium being preferable.

[0018] In the silicon oxide layer (B) described above, the average concentration of alkali metal atoms in the region at a depth of 0.1 to 0.3 nm from the surface in contact with the water-repellent and oil-repellent layer (C) is preferably 1.4 × 10⁻¹⁴. 18 atoms / cm 3 The above, more preferably 1.4 × 10 18 atoms / cm 3 The above 2.0 × 10 19 atoms / cm 3 Less than 3.7 × 10 18 atoms / cm 3 The above 1.8 × 10 19 atoms / cm 3 More preferably, 3.7 × 10 18 atoms / cm 3 The above 9.4 × 10 18 atoms / cm 3 The following are possible:

[0019] In the silicon oxide layer (B) described above, in a region where the depth from the surface in contact with the water-repellent and oil-repellent layer (C) is 0.1 to 0.3 nm, the proportion of sodium described above may be preferably 80 to 100 atomic percent, more preferably 90 to 100 atomic percent, and even more preferably 95 to 100 atomic percent, out of 100 atomic percent of the total amount of alkali metal atoms.

[0020] The average concentration of alkali metal atoms in the region at a depth of 0.1 to 0.3 nm from the surface in contact with the above-mentioned water- and oil-repellent layer (C) can be measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS).

[0021] The silicon oxide layer (B) has Cl in a region with a depth of 0.1 to 0.3 nm from the surface in contact with the water-repellent and oil-repellent layer (C). - , SO3 - NO3 - SO4 2- , PO3 - and PO4 3- Preferably, it contains one or more selected from the group consisting of Cl - , SO3 - and NO3 - It is more preferable to include one or more selected from the group consisting of NO3 - It is even more preferable to include

[0022] The above Cl - , SO3 - NO3 - SO4 2- , PO3 - and PO4 3- The content of one or more selected from the group consisting of the above may be preferably 1.0% to 20.0%, more preferably 1.0% to 10.0%, and even more preferably 1.0% to 5.0% with respect to the total count.

[0023] The above Cl - , SO3 - NO3 - SO4 2- , PO3 - and PO4 3- The content of one or more elements selected from the group consisting of these elements can be measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS).

[0024] In one embodiment, the silicon oxide layer (B) may be formed from a binder composition. Such a binder composition may preferably include a silicon oxide precursor, an acid, and an alkali metal salt.

[0025] Examples of silicon oxide precursors include silicic acid, partial condensates of silicic acid, alkali metal silicates, silane compounds having a hydrolyzable group bonded to a silicon atom, and partial hydrolyzable condensates of the silane compounds. Silicic acid and its partial condensates can be dehydrated and condensed to produce silicon oxide, while alkali metal silicates can be converted to silicic acid or its partial condensates using an acid or cation exchange resin, and the resulting silicic acid or partial condensates can be dehydrated and condensed to produce silicon oxide. Examples of hydrolyzable groups in silane compounds having a hydrolyzable group bonded to a silicon atom include alkoxy groups and chlorine atoms. The hydrolyzable group in the silane compound can be hydrolyzed to a hydroxyl group, and the resulting silanol compound can be dehydrated and condensed to produce silicon oxide. Examples of silane compounds having a hydrolyzable group bonded to a silicon atom include alkoxysilanes such as tetraalkoxysilanes and alkyltrialkoxysilanes, and tetrachlorosilanes.

[0026] The above-mentioned acid may be an inorganic acid or an organic acid.

[0027] Examples of the inorganic acids mentioned above include hydrochloric acid, sulfurous acid, nitric acid, sulfuric acid, phosphoric acid, and formic acid. Examples of the organic acids mentioned above include acetic acid.

[0028] The acid content may be preferably 0.01 moles to 10.0 moles, more preferably 0.02 moles to 5.0 moles, and even more preferably 0.05 moles to 1.0 mole, per mole of silicon atoms contained in the silicon oxide precursor. Having the acid content within this range makes it easier to control the concentration of alkali metal atoms in the silicon oxide layer (B).

[0029] The alkali metal salt described above may be any salt containing alkali metal ions. Examples of alkali metal ions contained in such alkali metal salts include lithium ions, sodium ions, and potassium ions, with sodium ions being preferred. Examples of alkali metal ions include chloride salts, sulfites, nitrates, sulfates, and phosphates containing these alkali metal ions, with chloride salts and nitrates being preferred. Sodium chloride and sodium nitrate are preferred as alkali metal salts.

[0030] The content of the alkali metal salt may be preferably 0.01 moles to 2.0 moles, more preferably 0.05 moles to 1.0 moles, and even more preferably 0.1 moles to 0.5 moles, per mole of silicon atoms contained in the silicon oxide precursor. Having the alkali metal salt content within this range makes it easier to control the concentration of alkali metal atoms in the silicon oxide layer (B).

[0031] The conjugate base in the above acid and the Cl contained in the above alkali metal salt. - , SO3 - NO3 - SO4 2- , PO3 - and PO4 3- The one or more selected from the group consisting of the above may be the same or different. In one embodiment, the conjugate base in the above acid and the Cl contained in the above alkali metal salt - , SO3 - NO3 - SO4 2- , PO3 - and PO4 3- One or more selected from the group consisting of the above are the same. In another embodiment, the conjugate base in the above acid and the Cl contained in the above alkali metal salt - , SO3 - NO3 - SO4 2- , PO3 - and PO4 3- It is different from one or more species selected from the group consisting of the following.

[0032] In the above binder composition, the total content of silicon dioxide precursor, acid, and alkali metal salt may be preferably 1% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 50% by mass or less, and even more preferably 10% by mass or more and 40% by mass or less, based on the total amount of the binder composition.

[0033] In a preferred embodiment, the binder composition may further contain a solvent. A binder composition containing a solvent is also called a liquid binder composition.

[0034] Examples of the above solvents include water; alcohols such as methanol, ethanol, iso-propanol, 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; and amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. Among these, water and alcohols are preferred, with methanol, ethanol, iso-propanol, n-butanol, isobutanol, tert-butanol, and sec-butanol being preferred, and water, methanol, ethanol, and iso-propanol being preferred.

[0035] In the above liquid binder composition, the solvent content may preferably be 90.0% by mass or more and 99.95% by mass or less, more preferably 95.0% by mass or more and 99.90% by mass or less, and even more preferably 98.0% by mass or more and 99.50% by mass or less.

[0036] The silicon dioxide layer (B) can be formed by applying the binder composition to the surface of the substrate (A). The coating method is not particularly limited. For example, wet coating and dry coating methods can be used.

[0037] Examples of wet coating methods include immersion coating, spin coating, flow coating, spray coating, roll coating, gravure coating, wipe coating, squeegee coating, die coating, inkjet, cast coating, Langmuir-Bludget method, and similar methods.

[0038] 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 beams, high-frequency heating using microwaves, ion beams, and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.

[0039] Furthermore, coating using the atmospheric pressure plasma method is also possible.

[0040] In one aspect, when using the wet coating method, the solvent is, for example, R 90 Compounds represented by -OH can be used. 90 is a monovalent organic group, preferably C 1-20 Alkyl alkyl group or C 3-20 These are alkylene groups, and these groups may be substituted with one or more substituents. Examples of substituents include hydroxyl groups, -OR 91 (Here, R 91 is C 1-10 Alkyl alkyl group, preferably C 1-3 Examples include alkyl groups (for example, a methyl group).

[0041] When using the dry coating method, the binder composition may be subjected to the dry coating method as is, or it may be diluted with the solvent described above before being subjected to the dry coating method.

[0042] The formation of the silicon oxide layer (B) is preferably carried out such that the silicon oxide precursor is present in the layer together with an acid acting as a catalyst for hydrolysis and dehydration condensation. For convenience, in the case of the wet coating method, the binder composition may be diluted with a solvent, and the catalyst may be added to the diluted binder composition immediately before application to the substrate surface. In the case of the dry coating method, the binder composition with the catalyst added may be directly subjected to vapor deposition (usually by vacuum deposition), or a pellet-like material impregnated with the catalyst-added surface treatment agent may be used for vapor deposition (usually by vacuum deposition).

[0043] The above binder composition may contain catalysts other than acids. Such other catalysts may include any suitable base, transition metals (e.g., Ti, Ni, Sn, Zr, Al, B, etc.), sulfur-containing compounds having lone pairs of electrons in their molecular structure, or nitrogen-containing compounds (e.g., sulfoxide compounds, aliphatic amine compounds, aromatic amine compounds, phosphate amide compounds, amide compounds, urea compounds, etc.). Examples of base catalysts include ammonia, sodium hydroxide, potassium hydroxide, triethylamine, diethylamine, and other organic amines. Examples of transition metals, aliphatic amine compounds, and aromatic amine compounds are the same as those described above.

[0044] In a preferred embodiment, the thickness of the silicon oxide layer (B) may be preferably 1 to 50 nm, more preferably 1 to 30 nm, even more preferably 2 to 15 nm, and even more preferably 3 to 10 nm.

[0045] Water and oil repellent layer (C) The above water- and oil-repellent layer (C) is disposed on the above silicon oxide layer (B) and is formed from a silane compound containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded. The above silane compound contains a fluorine atom. Typically, such a silane compound may have a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded. The hydrolysis condensate of the above silane compound can be formed by the hydrolysis and / or condensation of such hydroxyl group or hydrolyzable group to form a siloxane bond (-Si-O-Si-).

[0046] The above-mentioned silane compound is a silane compound having a fluorine atom, and is preferably a silane compound containing a fluoropolyether group.

[0047] Preferably, the silane compound is of the following formula (1) or (2): [ka] [In formula: R F1 Each of them is independent of Rf 1 -R F -O q -and; R F2 -Rf 2 p -R F -O q -and; Rf 1 Each of these C atoms may be independently substituted with one or more fluorine atoms. 1-16 It is an alkyl group; Rf 2 C may be substituted with one or more fluorine atoms. 1-6 It is an alkylene group; R F Each of these is independently a divalent fluoropolyether group; p is either 0 or 1; q is either 0 or 1, independently of each other; R Si Each of these is independently a monovalent group containing a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a Si atom to which a monovalent organic group is bonded; at least one R Si This is a monovalent group containing a Si atom to which a hydroxyl group or hydrolyzable group is bonded; X A Each of these is independently a single bond or a 2-10 valent organic group; α is an integer between 1 and 9; β is an integer between 1 and 9; Each of the γ values ​​is an independent integer between 1 and 9. It is at least one silane compound represented by .

[0048] In the above equation (1), R F1 Each of them is independent of Rf 1 -R F -O q - is

[0049] In equation (2) above, R F2 -Rf 2 p -R F -O q - is

[0050] In the above formula, Rf 1 Each of these C atoms may be independently substituted with one or more fluorine atoms. 1-16 It is an alkyl group.

[0051] C may be substituted with one or more fluorine atoms as described above. 1-16 "C" in alkyl groups 1-16 The alkyl group may be linear or branched, preferably linear or branched C 1-6 Alkyl groups, especially C 1-3 It is an alkyl group, more preferably a linear C 1-6 Alkyl groups, especially C 1-3 It is an alkyl group.

[0052] The above Rf 1 Preferably, C is substituted with one or more fluorine atoms. 1-16 It is an alkyl group, more preferably CF2H-C1-15 A perfluoroalkylene group, more preferably C 1-16 It is a perfluoroalkyl group.

[0053] C above 1-16 The perfluoroalkyl group may be linear or branched, preferably linear or branched C 1-6 Perfluoroalkyl groups, especially C 1-3 A perfluoroalkyl group, more preferably a linear C group. 1-6 Perfluoroalkyl groups, especially C 1-3 Perfluoroalkyl groups, specifically -CF3, -CF2CF3, or -CF2CF2CF3.

[0054] In the above formula, Rf 2 C may be substituted with one or more fluorine atoms. 1-6 It is an alkylene group.

[0055] C may be substituted with one or more fluorine atoms as described above. 1-6 "C" in the alkylene group 1-6 The alkylene group may be linear or branched, preferably linear or branched C 1-3 An alkylene group, more preferably a linear C group 1-3 It is an alkylene group.

[0056] The above Rf 2 Preferably, C is substituted with one or more fluorine atoms. 1-6 It is an alkylene group, and more C 1-6 A perfluoroalkylene group, more preferably C 1-3 It is a perfluoroalkylene group.

[0057] C above 1-6 The perfluoroalkylene group may be linear or branched, preferably linear or branched C 1-3 A perfluoroalkylene group, more preferably a linear C 1-3The perfluoroalkylene group is specifically -CF2-, -CF2CF2-, or -CF2CF2CF2-.

[0058] In the above formula, p is either 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.

[0059] In the above equation, q is either 0 or 1, independently of the other. In one embodiment, q is 0. In another embodiment, q is 1.

[0060] In the above equations (1) and (2), R F These are, independently, divalent fluoropolyether groups.

[0061] R F Preferably, the formula is: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - [In formula: R Fa These are, independently, a hydrogen atom, a fluorine atom, or a chlorine atom. a, b, c, d, e, and f are each independent integers between 0 and 200, and the sum of a, b, c, d, e, and f is 1 or greater. The order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the expression. However, all R Fa If is a hydrogen atom or a chlorine atom, then at least one of a, b, c, e, and f is 1 or more. It is a base represented by .

[0062] R Fa is preferably a hydrogen atom or a fluorine atom, and more preferably a fluorine atom. However, all R FaIf is a hydrogen atom or a chlorine atom, then at least one of a, b, c, e, and f is 1 or more.

[0063] a, b, c, d, e, and f may preferably be independent integers between 0 and 100.

[0064] 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.

[0065] These repeating units may be linear, branched, or contain ring structures. For example, -(OC6F 12 )- may also be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. -(OC5F 10 )- may be -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- may be -(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))-. -(OC3F6)-(that is, in the above formula, R Fa(where is a fluorine atom) may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-. -(OC2F4)- may be any of -(OCF2CF2)- and -(OCF(CF3))-.

[0066] The above ring structure may be a three-membered ring, a four-membered ring, a five-membered ring, or a six-membered ring.

[0067] [ka] [In the formula, * indicates a bonding position.]

[0068] The above ring structure may preferably be a four-membered ring, a five-membered ring, or a six-membered ring, more preferably a four-membered ring or a six-membered ring.

[0069] The repeating units having a ring structure may preferably be the following units.

[0070] [ka] [In the formula, * indicates a bonding position.]

[0071] In one embodiment, the repeating unit is linear. By making the repeating unit linear, the surface slipperiness, wear resistance, etc., of the surface treatment layer can be improved.

[0072] In one embodiment, the repeating unit is branched and chain-like. By making the repeating unit branched and chain-like, the coefficient of dynamic friction of the surface treatment layer can be increased.

[0073] In one embodiment, R F Each of these is an independent group that can be represented by one of the following equations (f1) to (f5). -(OC3F6) d -(OC2F4) e - (f1) [In the formula, d is an integer between 1 and 200, and e is either 0 or 1.] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2) [In the formula, c and d are independent integers between 0 and 30, and e and f are independent integers between 1 and 200.] The sum of c, d, e, and f is 2 or greater. The order of existence of each repeating unit, denoted by the subscripts c, d, e, or f and enclosed in parentheses, is arbitrary within the expression. -(R 6 -R 7 ) g - (f3) [In the formula, R 6 This is OCF2 or OC2F4, R 7 OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It is a group selected from these groups, or a combination of two or three groups selected independently from these groups. g is an integer between 2 and 100. -(R 6 -R 7 ) g -R r -(R 7’ -R 6’ ) g’ - (f4) [In the formula, R 6 This is OCF2 or OC2F4, R 7 OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It is a group selected from these groups, or a combination of two or three groups selected independently from these groups. R 6’ This is OCF2 or OC2F4, R 7’ OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12It is a group selected from these groups, or a combination of two or three groups selected independently from these groups. g is an integer between 2 and 100. g' is an integer between 2 and 100. R r teeth,

[0074] [ka] (In the formula, * indicates the bonding position.) That is. -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5) [In the formula, e is an integer between 1 and 200, a, b, c, d, and f are each independent integers between 0 and 200, and the order of existence 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 - (f6) [In the formula, f is an integer between 1 and 200, a, b, c, d, and e are each independent integers between 0 and 200, and the order of existence of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.]

[0075] In the above formula (f1), d is preferably an integer between 5 and 200, more preferably between 10 and 100, and even more preferably between 15 and 50, for example between 25 and 35. In the above formula (f1), OC3F6 is preferably (OCF2CF2CF2), (OCF(CF3)CF2), or (OCF2CF(CF3)), and more preferably (OCF2CF2CF2). In the above formula (f1), (OC2F4) is preferably (OCF2CF2) or (OCF(CF3)), and more preferably (OCF2CF2). In one embodiment, e is 0. In another embodiment, e is 1.

[0076] In the above formula (f2), e and f are each an integer, preferably between 5 and 200, more preferably between 10 and 200. The sum of c, d, e, and f is preferably 5 or greater, more preferably 10 or greater, and may be, for example, 15 or greater or 20 or greater. In one embodiment, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f - is the base represented by -. In another embodiment, formula (f2) is -(OC2F4) e -(OCF2) f It may also be represented as a base by -.

[0077] In the above equation (f3), R 6 Preferably, it is OC2F4. In (f3) above, R 7Preferably, the group is selected from OC2F4, OC3F6, and OC4F8, or a combination of two or three groups independently selected from these groups, and 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, but examples include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, and -OC Examples include 2F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -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 The chain may be either linear or branched, and is preferably linear. In this embodiment, the above formula (f3) is preferably -(OC2F4-OC3F6) g -or-(OC2F4-OC4F8) g - is

[0078] In the above equation (f4), R 6 , R 7 And g have the same meaning as described in the above formula (f3) and have the same characteristics. 6’ , R 7’ and g' are R as described in formula (f3) above, respectively. 6 , R 7 And g are synonymous and have similar characteristics. r Preferably,

[0079] [ka] [In the formula, * indicates a bonding position.] and, more

[0080] [ka] [In the formula, * indicates a bonding position.] That is the case.

[0081] In the above formula (f5), e is preferably an integer between 1 and 100, more preferably between 5 and 100. The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example between 10 and 100.

[0082] In the above formula (f6), f is preferably an integer between 1 and 100, more preferably between 5 and 100. The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example between 10 and 100.

[0083] In one embodiment, the above R F This is the group represented by the above formula (f1).

[0084] In one embodiment, the above R F This is the group represented by the above formula (f2).

[0085] In one embodiment, the above R F This is the group represented by the above formula (f3).

[0086] In one embodiment, the above R F This is the group represented by the above formula (f4).

[0087] In one embodiment, the above R F This is the group represented by the above formula (f5).

[0088] In one embodiment, the above R F This is the group represented by the above formula (f6).

[0089] The above R F In this compound, the ratio of e to f (hereinafter referred to as the "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, wear resistance, and chemical resistance (e.g., resistance to artificial sweat) of the surface treatment layer obtained from this compound are further improved. The smaller the e / f ratio, the better the slipperiness and wear resistance 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 enhanced. The larger the e / f ratio, the better the stability of the compound.

[0090] In the above silane compound, R F1 and R F2 The number-average molecular weight of the part 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. In this specification, R F1 and R F2 The number-average molecular weight is, 19 The value shall be measured by 1F-NMR.

[0091] In another embodiment, R F1 and R F2 The number-average molecular weight of the part may be 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, and even more preferably 2,000 to 10,000, for example, 3,000 to 6,000.

[0092] In another embodiment, R F1 and R F2 The number-average molecular weight of the part may be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0093] In the above equations (1) and (2), R SiEach is independently a monovalent group containing a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group bonded to a Si atom, and at least one R Si This is a monovalent group containing a Si atom to which a hydroxyl group or hydrolyzable group is bonded.

[0094] Here, "hydrolyzable group" refers to a group that can undergo hydrolysis, that is, a group that can be removed from the main skeleton of a compound by hydrolysis. Examples of hydrolyzable groups include -OR j , -OCOR j , -ON=CR j 2. -NR j 2, -NHR j , -NCO, halogen (in these formulas, R j C is either substituted or non-substituted. 1-4 Examples include (showing an alkyl group).

[0095] In a preferred embodiment, R Si This is a monovalent group containing a Si atom to which a hydroxyl group or hydrolyzable group is bonded.

[0096] In a preferred embodiment, R Si This is expressed by the following formulas (S1), (S2), (S3), or (S4): [ka] It is a base represented by .

[0097] In the above formula, R 11 These are, independently, hydroxyl groups or hydrolyzable groups.

[0098] R 11 Preferably, each of these is independently a hydrolyzable group.

[0099] R 11 Preferably, each is independently of -OR j , -OCOR j , -ON=CR j 2. -NR j 2, -NHR j, -NCO, or halogen (wherein R in these formulas) j C is either substituted or non-substituted. 1-4 (representing an alkyl group), more preferably OR j (That is, an alkoxy group). j Examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl groups; and substituted alkyl groups such as chloromethyl groups. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R j is a methyl group, and in another embodiment, R j This is an ethyl group.

[0100] In the above formula, R 12 Each of these is independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0101] R 12 In this, the monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 An alkyl group, more preferably a methyl group.

[0102] In the above formula, n1 is (SiR 11 n1 R 12 3-n1 Each unit is an independent integer between 0 and 3. However, R Si If the group is represented by formula (S1) or (S2), then the terminal R of formulas (1) and (2) Si In the part (hereinafter also simply referred to as the "terminal part" of equations (1) and (2)), n1 is 1 to 3 (SiR 11 n1 R 12 3-n1 There is at least one unit. That is, in such terminal parts, not all n1s are 0 at the same time. In other words, in the terminal parts of formulas (1) and (2), there is at least one Si atom to which a hydroxyl group or hydrolyzable group is bonded.

[0103] n1 is (SiR 11 n1 R 12 3-n1 Each unit is independently an integer, preferably between 1 and 3, more preferably between 2 and 3, and even more preferably 3.

[0104] In the above formula, X 11 Each of these is independently a single bond or a divalent organic group. Such a divalent organic group is preferably -R 28 -O x -R 29 -(In the formula, R 28 and R 29 Each of these is independently a single bond or C 1-20 It is an alkylene group, and x is 0 or 1. 1-20 The alkylene group may be linear or branched, but is preferably linear. 1-20 The alkylene group is preferably C 1-10 Alkylene group, more preferably C 1-6 Alkylene group, more preferably C 1-3 It is an alkylene group.

[0105] In one embodiment, X 11 These are, independently, -C 1-6 Alkylene-OC 1-6 Alkilen- or -OC 1-6 It is alkylene-.

[0106] In a preferred embodiment, X 11 Each of these is independently a single bond or a linear chain of carbon atoms. 1-6 An alkylene group, preferably a single bond or a linear C bond. 1-3 Alkylene group, more preferably single bond or linear carbon 1-2 An alkylene group, more preferably a linear carbon group. 1-2 It is an alkylene group.

[0107] In the above formula, R 13Each of these is independently 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 linear or branched, but is preferably linear.

[0108] In a preferred embodiment, R 13 Each of these is independently a hydrogen atom or a linear C 1-6 It is an alkyl group, preferably a hydrogen atom or a linear C 1-3 The alkyl group is preferably a hydrogen atom or a methyl group.

[0109] In the above equations, each t is an independent integer greater than or equal to 2.

[0110] In a preferred embodiment, t is an integer between 2 and 10, preferably between 2 and 6, independently of each other.

[0111] In the above formula, R 14 Each of these is independently a hydrogen atom, a halogen atom, or -X 11 -SiR 11 n1 R 12 3-n1 The halogen atom is preferably an iodine atom, a chlorine atom, or a fluorine atom, and more preferably a fluorine atom. In a preferred embodiment, R 14 This is a hydrogen atom.

[0112] In the above formula, R 15 Each of these is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkylene oxy group having 1 to 6 carbon atoms.

[0113] In one embodiment, R 15 These are, independently, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkylene oxy group having 1 to 6 carbon atoms.

[0114] In a preferred embodiment, R 15 It is a single bond.

[0115] In one embodiment, equation (S1) is given by the following equation (S1-a). [ka] [In the formula, R 11 , R 12 , R 13 , X 11 , and n1 are equivalent to the description in the above formula (S1); t1 and t2 are each independent integers of 1 or more, preferably integers between 1 and 10, more preferably integers between 2 and 10, for example, integers between 1 and 5 or integers between 2 and 5; The order in which each repeating unit, denoted by t1 and t2 and enclosed in parentheses, exists is arbitrary within the expression.

[0116] In a preferred embodiment, formula (S1) is the following formula (S1-b). [ka] [In the formula, R 11 , R 12 , R 13 , X 11 n1 and t have the same meaning as described in the above formula (S1).

[0117] In the above formula, R a1 These are, independently, -Z 1 -SiR 21 p1 R 22 q1 R 23 r1 That is the case.

[0118] The above Z 1 Each of these is independently an oxygen atom or a divalent organic group. (Note: Z follows) 1 The structure described as follows is (SiR 21 p1 R 22 q1 R 23 r1 ) joins.

[0119] In a preferred embodiment, Z 1 It is a divalent organic group.

[0120] In a preferred embodiment, Z 1 is, Z 1 It does not contain any element that forms a siloxane bond with the Si atom to which it is bonded. Preferably, in formula (S3), (Si-Z 1 -Si) does not contain a siloxane bond.

[0121] The above Z 1 Preferably, C 1-6 Alkylene group, -(CH2) z1 -O-(CH2) z2 -(wherein z1 is an integer between 0 and 6, e.g., an integer between 1 and 6, and z2 is an integer between 0 and 6, e.g., an integer between 1 and 6) or -(CH2) z3 -Phenylene-(CH2) z4 -(wherein z3 is an integer from 0 to 6, for example, an integer from 1 to 6, and z4 is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may include, for example, a fluorine atom, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, and C 2-6 The alkynyl group may be substituted with one or more substituents selected from the alkynyl group, but is preferably unsubstituted.

[0122] In a preferred embodiment, Z 1 C 1-6 Alkylene group or -(CH2) z3 -Phenylene-(CH2) z4 -, preferably -phenylene-(CH2) z4 - is Z 1 If the group is such that it can have higher light resistance, especially UV resistance.

[0123] In another preferred embodiment, the above Z 1 C 1-3 It is an alkylene group. In one embodiment, Z 1This could be -CH2CH2CH2-. In another embodiment, Z 1 It can be -CH2CH2-.

[0124] The above R 21 These are, independently, -Z 1’ -SiR 21’ p1’ R 22’ q1’ R 23’ r1’ That is the case.

[0125] The above Z 1’ Each of these is independently an oxygen atom or a divalent organic group. (Note: Z follows) 1’ The structure described as follows is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ ) joins.

[0126] In a preferred embodiment, Z 1’ It is a divalent organic group.

[0127] In a preferred embodiment, Z 1’ is, Z 1’ It does not contain any element that forms a siloxane bond with the Si atom to which it is bonded. Preferably, in formula (S3), (Si-Z 1’ -Si) does not contain a siloxane bond.

[0128] The above Z 1’ Preferably, C 1-6 Alkylene group, -(CH2) z1’ -O-(CH2) z2’ -(wherein z1' is an integer between 0 and 6, e.g., an integer between 1 and 6, and z2' is an integer between 0 and 6, e.g., an integer between 1 and 6) or -(CH2) z3’ -Phenylene-(CH2) z4’ -(wherein z3' is an integer between 0 and 6, for example between 1 and 6, and z4' is an integer between 0 and 6, for example between 1 and 6). Such C 1-6The alkylene group may be linear or branched, but is preferably linear. These groups may include, for example, a fluorine atom, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, and C 2-6 The alkynyl group may be substituted with one or more substituents selected from the alkynyl group, but is preferably unsubstituted.

[0129] In a preferred embodiment, Z 1’ C 1-6 Alkylene group or -(CH2) z3’ -Phenylene-(CH2) z4’ -, preferably -phenylene-(CH2) z4’ - is Z 1’ If the group is such that it can have higher light resistance, especially UV resistance.

[0130] In another preferred embodiment, the above Z 1’ C 1-3 It is an alkylene group. In one embodiment, Z 1’ This could be -CH2CH2CH2-. In another embodiment, Z 1’ It can be -CH2CH2-.

[0131] The above R 21’ These are, independently, -Z 1” -SiR 22” q1” R 23” r1” That is the case.

[0132] The above Z 1” Each of these is independently an oxygen atom or a divalent organic group. (Note: Z follows) 1” The structure described as follows is (SiR 22” q1” R 23” r1” ) joins.

[0133] In a preferred embodiment, Z 1” It is a divalent organic group.

[0134] In a preferred embodiment, Z 1” is, Z 1” It does not contain any element that forms a siloxane bond with the Si atom to which it is bonded. Preferably, in formula (S3), (Si-Z 1” -Si) does not contain a siloxane bond.

[0135] The above Z 1” Preferably, C 1-6 Alkylene group, -(CH2) z1” -O-(CH2) z2” -(wherein z1'' is an integer between 0 and 6, e.g., an integer between 1 and 6, and z2'' is an integer between 0 and 6, e.g., an integer between 1 and 6) or -(CH2) z3” -Phenylene-(CH2) z4” -(wherein z3'' is an integer from 0 to 6, for example, an integer from 1 to 6, and z4'' is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may include, for example, a fluorine atom, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, and C 2-6 The alkynyl group may be substituted with one or more substituents selected from the alkynyl group, but is preferably unsubstituted.

[0136] In a preferred embodiment, Z 1” C 1-6 Alkylene group or -(CH2) z3” -Phenylene-(CH2) z4” -, preferably -phenylene-(CH2) z4” - is Z 1” If the group is such that it can have higher light resistance, especially UV resistance.

[0137] In another preferred embodiment, the above Z 1” C 1-3 It is an alkylene group. In one embodiment, Z 1” This could be -CH2CH2CH2-. In another embodiment, Z 1” It can be -CH2CH2-.

[0138] The above R 22” These are, independently, hydroxyl groups or hydrolyzable groups.

[0139] The above R 22” Preferably, each of these is independently a hydrolyzable group.

[0140] The above R 22” Preferably, each is independently of -OR j , -OCOR j , -ON=CR j 2. -NR j 2, -NHR j , -NCO, or halogen (wherein R in these formulas) j C is either substituted or non-substituted. 1-4 (representing an alkyl group), more preferably OR j (That is, an alkoxy group). j Examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl groups; and substituted alkyl groups such as chloromethyl groups. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R j is a methyl group, and in another embodiment, R j This is an ethyl group.

[0141] The above R 23” Each of these is independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0142] The above R 23” In this, the monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 An alkyl group, more preferably a methyl group.

[0143] Each of the above q1'' is an independent integer between 0 and 3, and each of the above r1'' is an independent integer between 0 and 3. The sum of q1'' and r1'' is (SiR 22”q1” R 23” r1” In units of 3, it is 3.

[0144] The above q1'' is (SiR 22” q1” R 23” r1” Each unit is independently an integer, preferably between 1 and 3, more preferably between 2 and 3, and even more preferably 3.

[0145] The above R 22’ These are, independently, hydroxyl groups or hydrolyzable groups.

[0146] R 22’ Preferably, each of these is independently a hydrolyzable group.

[0147] R 22’ Preferably, each is independently of -OR j , -OCOR j , -ON=CR j 2. -NR j 2, -NHR j , -NCO, or halogen (wherein R in these formulas) j C is either substituted or non-substituted. 1-4 (representing an alkyl group), more preferably OR j (That is, an alkoxy group). j Examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl groups; and substituted alkyl groups such as chloromethyl groups. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R j is a methyl group, and in another embodiment, R j This is an ethyl group.

[0148] The above R 23’ Each of these is independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0149] R23’ In this, the monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 An alkyl group, more preferably a methyl group.

[0150] Each of the above p1' is an independent integer between 0 and 3, each of the q1' is an independent integer between 0 and 3, and each of the r1' is an independent integer between 0 and 3. Note that the sum of p', q1' and r1' is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ In units of 3, it is 3.

[0151] In one embodiment, p1' is 0.

[0152] In one embodiment, p1' is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ Each unit may independently be an integer from 1 to 3, an integer from 2 to 3, or 3. In a preferred embodiment, p1' is 3.

[0153] In one embodiment, q1' is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ Each unit is an integer between 1 and 3, preferably between 2 and 3, and more preferably 3.

[0154] In one embodiment, p1' is 0 and q1' is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ Each unit is an integer between 1 and 3, preferably between 2 and 3, and more preferably 3.

[0155] The above R22 These are, independently, hydroxyl groups or hydrolyzable groups.

[0156] R 22 Preferably, each of these is independently a hydrolyzable group.

[0157] R 22 Preferably, each is independently of -OR j , -OCOR j , -ON=CR j 2. -NR j 2, -NHR j , -NCO, or halogen (wherein R in these formulas) j C is either substituted or non-substituted. 1-4 (representing an alkyl group), more preferably OR j (That is, an alkoxy group). j Examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl groups; and substituted alkyl groups such as chloromethyl groups. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R j is a methyl group, and in another embodiment, R j This is an ethyl group.

[0158] The above R 23 Each of these is independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0159] R 23 In this, the monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 An alkyl group, more preferably a methyl group.

[0160] Each of the above p1 is an independent integer between 0 and 3, each of the q1 is an independent integer between 0 and 3, and each of the r1 is an independent integer between 0 and 3. Note that the sum of p1, q1 and r1 is (SiR 21 p1 R22 q1 R 23 r1 In units of 3, it is 3.

[0161] In one embodiment, p1 is 0.

[0162] In one embodiment, p1 is (SiR 21 p1 R 22 q1 R 23 r1 Each unit may independently be an integer from 1 to 3, an integer from 2 to 3, or 3. In a preferred embodiment, p1 is 3.

[0163] In one mode, q1 is (SiR 21 p1 R 22 q1 R 23 r1 Each unit is an integer between 1 and 3, preferably between 2 and 3, and more preferably 3.

[0164] In one embodiment, p1 is 0 and q1 is (SiR 21 p1 R 22 q1 R 23 r1 Each unit is an integer between 1 and 3, preferably between 2 and 3, and more preferably 3.

[0165] In the above formula, R b1 These are, independently, hydroxyl groups or hydrolyzable groups.

[0166] The above R b1 Preferably, each of these is independently a hydrolyzable group.

[0167] The above R b1 Preferably, each is independently of -OR j , -OCOR j , -ON=CR j 2. -NRj 2, -NHR j , -NCO, or halogen (wherein R in these formulas) j C is either substituted or non-substituted. 1-4 (representing an alkyl group), more preferably OR j (That is, an alkoxy group). j Examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl groups; and substituted alkyl groups such as chloromethyl groups. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R j is a methyl group, and in another embodiment, R j This is an ethyl group.

[0168] In the above formula, R c1 Each of these is independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0169] The above R c1 In this, the monovalent organic group is preferably C 1-20 It is an alkyl group, more preferably C 1-6 An alkyl group, more preferably a methyl group.

[0170] Each of the above k1 is an independent integer between 0 and 3, each l1 is an independent integer between 0 and 3, and each m1 is an independent integer between 0 and 3. Note that the sum of k1, l1 and m1 is (SiR a1 k1 R b1 l1 R c1 m1 In units of 3, it is 3.

[0171] In one embodiment, k1 is (SiR a1 k1 R b1 l1 R c1 m1Each unit is an integer between 1 and 3, preferably 2 or 3, more preferably 3. In a preferred embodiment, k1 is 3.

[0172] In the above equations (1) and (2), R Si When is a group represented by formula (S3), preferably, at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded are present in the terminal portions of formulas (1) and (2).

[0173] In a preferred embodiment, the group represented by formula (S3) is -Z 1 -SiR 22 q1 R 23 r1 (In the formula, q1 is an integer between 1 and 3, preferably 2 or 3, more preferably 3, and r1 is an integer between 0 and 2.) -Z 1’ -SiR 22’ q1’ R 23’ r1’ (In the formula, q1' is an integer between 1 and 3, preferably 2 or 3, more preferably 3, and r1' is an integer between 0 and 2.) or -Z 1” -SiR 22” q1” R 23” r1” (wherein the formula, q1'' is an integer between 1 and 3, preferably 2 or 3, more preferably 3, and r1'' is an integer between 0 and 2.) Z 1 , Z 1’ , Z 1” , R 22 , R 23 , R 22’ , R 23’ , R 22” , and R 23” This is synonymous with the above.

[0174] In a preferred embodiment, in formula (S3), R 21’ If present, at least one, preferably all R 21’ In this, q1'' is an integer between 1 and 3, preferably 2 or 3, more preferably 3.

[0175] In a preferred embodiment, in formula (S3), R 21 If present, at least one, preferably all R 21 In this case, p1' is 0, and q1' is an integer between 1 and 3, preferably 2 or 3, more preferably 3.

[0176] In a preferred embodiment, in formula (S3), R a1 If present, at least one, preferably all R a1 In this case, p1 is 0, and q1 is an integer between 1 and 3, preferably 2 or 3, more preferably 3.

[0177] 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.

[0178] R d1 These are, independently, -Z 2 -CR 31 p2 R 32 q2 R 33 r2 That is the case.

[0179] Z 2 Each of these is independently a single bond, an oxygen atom, or a divalent organic group. (Note: Z follows) 2 The structure described as follows is (CR) on the right side. 31 p2 R 32 q2 R 33 r2 ) joins.

[0180] In a preferred embodiment, Z 2 It is a divalent organic group.

[0181] The above Z 2 Preferably, C 1-6 Alkylene group, -(CH2) z5 -O-(CH2) z6-(wherein z5 is an integer between 0 and 6, e.g., an integer between 1 and 6, and z6 is an integer between 0 and 6, e.g., an integer between 1 and 6) or -(CH2) z7 -Phenylene-(CH2) z8 -(wherein z7 is an integer from 0 to 6, for example, an integer from 1 to 6, and z8 is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may include, for example, a fluorine atom, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, and C 2-6 The alkynyl group may be substituted with one or more substituents selected from the alkynyl group, but is preferably unsubstituted.

[0182] In a preferred embodiment, Z 2 C 1-6 Alkylene group or -(CH2) z7 -Phenylene-(CH2) z8 -, preferably -phenylene-(CH2) z8 - is Z 2 If the group is such that it can have higher light resistance, especially UV resistance.

[0183] In another preferred embodiment, the above Z 2 C 1-3 It is an alkylene group. In one embodiment, Z 2 This could be -CH2CH2CH2-. In another embodiment, Z 2 It can be -CH2CH2-.

[0184] R 31 These are, independently, -Z 2’ -CR 32’ q2’ R 33’ r2’ That is the case.

[0185] Z 2’ Each of these is independently a single bond, an oxygen atom, or a divalent organic group. (Note: Z follows) 2’ The structure described as follows is (CR) on the right side. 32’q2’ R 33’ r2’ ) joins.

[0186] The above Z 2’ Preferably, C 1-6 Alkylene group, -(CH2) z5’ -O-(CH2) z6’ -(wherein z5' is an integer between 0 and 6, e.g., an integer between 1 and 6, and z6' is an integer between 0 and 6, e.g., an integer between 1 and 6) or -(CH2) z7’ -Phenylene-(CH2) z8’ -(wherein z7' is an integer from 0 to 6, for example, an integer from 1 to 6, and z8' is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may include, for example, a fluorine atom, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, and C 2-6 The alkynyl group may be substituted with one or more substituents selected from the alkynyl group, but is preferably unsubstituted.

[0187] In a preferred embodiment, Z 2’ C 1-6 Alkylene group or -(CH2) z7’ -Phenylene-(CH2) z8’ -, preferably -phenylene-(CH2) z8’ - is Z 2’ If the group is such that it can have higher light resistance, especially UV resistance.

[0188] In another preferred embodiment, the above Z 2’ C 1-3 It is an alkylene group. In one embodiment, Z 2’ This could be -CH2CH2CH2-. In another embodiment, Z 2’ It can be -CH2CH2-.

[0189] The above R 32’ These are, independently, -Z 3 -SiR 34n2 R 35 3-n2 That is the case.

[0190] The above Z 3 Each of these is independently a single bond, an oxygen atom, or a divalent organic group. (Note: Z follows) 3 The structure described as follows is (SiR 34 n2 R 35 3-n2 ) joins.

[0191] In one embodiment, Z 3 It is an oxygen atom.

[0192] In one embodiment, Z 3 It is a divalent organic group.

[0193] The above Z 3 Preferably, C 1-6 Alkylene group, -(CH2) z5” -O-(CH2) z6” -(wherein z5'' is an integer between 0 and 6, e.g., an integer between 1 and 6, and z6'' is an integer between 0 and 6, e.g., an integer between 1 and 6) or -(CH2) z7” -Phenylene-(CH2) z8” -(wherein z7'' is an integer from 0 to 6, for example, an integer from 1 to 6, and z8'' is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may include, for example, a fluorine atom, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, and C 2-6 The alkynyl group may be substituted with one or more substituents selected from the alkynyl group, but is preferably unsubstituted.

[0194] In a preferred embodiment, Z 3 C 1-6 Alkylene group or -(CH2) z7” -Phenylene-(CH2) z8” -, preferably -phenylene-(CH2) z8”- is Z 3 If the group is such that it can have higher light resistance, especially UV resistance.

[0195] In another preferred embodiment, the above Z 3 C 1-3 It is an alkylene group. In one embodiment, Z 3 This could be -CH2CH2CH2-. In another embodiment, Z 3 It can be -CH2CH2-.

[0196] The above R 34 These are, independently, hydroxyl groups or hydrolyzable groups.

[0197] R 34 Preferably, each of these is independently a hydrolyzable group.

[0198] R 34 Preferably, each is independently of -OR j , -OCOR j , -ON=CR j 2. -NR j 2, -NHR j , -NCO, or halogen (wherein R in these formulas) j C is either substituted or non-substituted. 1-4 (representing an alkyl group), more preferably OR j (That is, an alkoxy group). j Examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl groups; and substituted alkyl groups such as chloromethyl groups. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R j is a methyl group, and in another embodiment, R j This is an ethyl group.

[0199] The above R 35 Each of these is independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0200] In the above R 35 , the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, still more preferably a methyl group.

[0201] In the above formula, n2 is, for each (SiR 34 n2 R 35 3-n2 ) unit, independently an integer of 0 to 3. However, when R Si is a group represented by the formula (S4), at the terminal portions of the formula (1) and the formula (2), n2 is 1 to 3, and at least one (SiR 34 n2 R 35 3-n2 ) unit exists. That is, in such terminal portions, all n2 do not simultaneously become 0. In other words, at the terminal portions of the formula (1) and the formula (2), at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded exists.

[0202] n2 is, for each (SiR 34 n2 R 35 3-n2 ) unit, independently preferably an integer of 1 to 3, more preferably 2 to 3, still more preferably 3.

[0203] In the above R 33’ , each is independently a hydrogen atom, a hydroxyl group or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

[0204] In the above R 33’ , the monovalent organic group is preferably a C 1-20 alkyl group or -(C s H 2s ) t1 -(O-C s H 2s ) t2H (where s is an integer from 1 to 6, preferably an integer from 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer from 1 to 20, preferably an integer from 2 to 10, more preferably an integer from 2 to 6). More preferably C 1-20 alkyl group, even more preferably C 1-6 alkyl group, particularly preferably a methyl group.

[0205] In one embodiment, R 33’ is a hydroxyl group.

[0206] In another embodiment, R 33’ is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.

[0207] Each of the above q2' is independently an integer from 0 to 3, and each of the above r2' is independently an integer from 0 to 3. Incidentally, the sum of q2' and r2' is 3 in the (CR 32’ q2’ R 33’ r2’ ) unit.

[0208] q2' is independently, for each (CR 32’ q2’ R 33’ r2’ ) unit, preferably an integer from 1 to 3, more preferably 2 to 3, even more preferably 3.

[0209] Each R 32 is independently -Z 3 -SiR 34 n2 R 35 3-n2 . Such -Z 3 -SiR 34 n2 R 35 3-n2 is as defined for the above R 32’ .

[0210] Each of the above R 33Each of these is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such a monovalent organic group is a monovalent organic group other than the hydrolyzable group mentioned above.

[0211] The above R 33 In this, the monovalent organic group is preferably C 1-20 Alkyl or -(C s H 2s ) t1 -(OC s H 2s ) t2 H(wherein s is an integer from 1 to 6, preferably from 2 to 4; t1 is 1 or 0, preferably 0; t2 is an integer from 1 to 20, preferably from 2 to 10, more preferably from 2 to 6); and more preferably C 1-20 Alkyl alkyl groups, more preferably C 1-6 Alkyl groups, particularly preferably methyl groups.

[0212] In one embodiment, R 33 This is a hydroxyl group.

[0213] In another embodiment, R 33 This is a monovalent organic group, preferably C 1-20 It is an alkyl group, more preferably C 1-6 It is an alkyl group.

[0214] Each of the above p2 values ​​is an independent integer between 0 and 3, each of the q2 values ​​is an independent integer between 0 and 3, and each of the r2 values ​​is an independent integer between 0 and 3. The sum of p2, q2, and r2 is (CR 31 p2 R 32 q2 R 33 r2 In units of 3, it is 3.

[0215] In one embodiment, p2 is 0.

[0216] In one embodiment, p2 is (CR 31 p2 R 32 q2 R33 r2 ) Independently for each unit, it may be an integer from 1 to 3, an integer from 2 to 3, or 3. In a preferred embodiment, p2 is 3.

[0217] In one embodiment, q2 is (CR 31 p2 R 32 q2 R 33 r2 ) Independently for each unit, it is an integer from 1 to 3, preferably an integer from 2 to 3, more preferably 3.

[0218] In one embodiment, p2 is 0 and q2 is (CR 31 p2 R 32 q2 R 33 r2 ) Independently for each unit, it is an integer from 1 to 3, preferably an integer from 2 to 3, even more preferably 3.

[0219] The above R e1 are each independently -Z 3 -SiR 34 n2 R 35 3-n2 That is. Such -Z 3 -SiR 34 n2 R 35 3-n2 is as defined in the above R 32’ and has the same meaning.

[0220] The above R f1 are each independently a hydrogen atom, a hydroxyl group or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

[0221] The above R f1 in, the monovalent organic group is preferably a C 1-20 alkyl group or -(C s H 2s ) t1 -(O-C s H 2s )t2 H(wherein s is an integer from 1 to 6, preferably from 2 to 4; t1 is 1 or 0, preferably 0; t2 is an integer from 1 to 20, preferably from 2 to 10, more preferably from 2 to 6); and more preferably C 1-20 Alkyl alkyl groups, more preferably C 1-6 Alkyl groups, particularly preferably methyl groups.

[0222] In one embodiment, R f1 This is a hydroxyl group.

[0223] In another embodiment, R f1 This is a monovalent organic group, preferably C 1-20 It is an alkyl group, more preferably C 1-6 It is an alkyl group.

[0224] Each of the above k2 is an independent integer between 0 and 3, each of the l2 is an independent integer between 0 and 3, and each of the m2 is an independent integer between 0 and 3. Note that the sum of k2, l2 and m2 is (CR d1 k2 R e1 l2 R f1 m2 In units of 3, it is 3.

[0225] In the above equations (1) and (2), R Si When is a group represented by formula (S4), preferably, at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded are present in the terminal portions of formulas (1) and (2).

[0226] In one embodiment, R Si When is a group represented by formula (S4), n2 is 1 to 3, preferably 2 or 3, more preferably 3 (SiR 34 n2 R 35 3-n2 The units are present in two or more units at each terminal portion of formula (1) and formula (2), for example, 2 to 27 units, preferably 2 to 9 units, more preferably 2 to 6 units, even more preferably 2 to 3 units, and particularly preferably 3 units.

[0227] In a preferred embodiment, in formula (S4), R 32’ If present, at least one, preferably all R 32’ In this, n2 is an integer between 1 and 3, preferably 2 or 3, more preferably 3.

[0228] In a preferred embodiment, in formula (S4), R 32 If present, at least one, preferably all R 32 In this, n2 is an integer between 1 and 3, preferably 2 or 3, more preferably 3.

[0229] In a preferred embodiment, in formula (S4), R e1 If present, at least one, preferably all R a1 In this, n2 is an integer between 1 and 3, preferably 2 or 3, more preferably 3.

[0230] 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.

[0231] The above R g1 and R h1 These are, independently, -Z 4 -SiR 11 n1 R 12 3-n1 , -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 , -Z 4 -CR d1 k2 R e1 l2 R f1 m2 Here, R 11 , R 12 , R a1 , R b2 , R c1, R d1 , R e1 , R f1 n1, k1, l1, m1, k2, l2, and m2 have the same meaning as above.

[0232] In a preferred embodiment, R g1 and R h1 These are, independently, -Z 4 -SiR 11 n1 R 12 3-n1 That is the case.

[0233] The above Z 4 Each of these is independently a single bond, an oxygen atom, or a divalent organic group. (Note: Z follows) 4 The structure described as follows is (SiR 11 n1 R 12 3-n1 ) joins.

[0234] In one embodiment, Z 4 It is an oxygen atom.

[0235] In one embodiment, Z 4 It is a divalent organic group.

[0236] The above Z 4 Preferably, C 1-6 Alkylene group, -(CH2) z5” -O-(CH2) z6” -(wherein z5'' is an integer between 0 and 6, e.g., an integer between 1 and 6, and z6'' is an integer between 0 and 6, e.g., an integer between 1 and 6) or -(CH2) z7” -Phenylene-(CH2) z8” -(wherein z7'' is an integer from 0 to 6, for example, an integer from 1 to 6, and z8'' is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may include, for example, a fluorine atom, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, and C 2-6The alkynyl group may be substituted with one or more substituents selected from the alkynyl group, but is preferably unsubstituted.

[0237] In a preferred embodiment, Z 4 C 1-6 Alkylene group or -(CH2) z7” -Phenylene-(CH2) z8” -, preferably -phenylene-(CH2) z8” - is Z 3 If the group is such that it can have higher light resistance, especially UV resistance.

[0238] In another preferred embodiment, the above Z 4 C 1-3 It is an alkylene group. In one embodiment, Z 4 This could be -CH2CH2CH2-. In another embodiment, Z 4 It can be -CH2CH2-.

[0239] In one embodiment, R Si These are groups represented by formulas (S2), (S3), (S4), or (S5). These compounds can form surface treatment layers with high surface slipperiness.

[0240] In one embodiment, R Si These are groups represented by formulas (S3), (S4), or (S5). Because these compounds have multiple hydrolyzable groups at one end, they can form a surface treatment layer that adheres strongly to the substrate and has high abrasion resistance.

[0241] In one embodiment, R Si This is a group represented by formula (S3) or (S4). Since these compounds may have multiple hydrolyzable groups branched from a single Si or C atom at one end, they can form a surface treatment layer with even higher wear resistance.

[0242] In one embodiment, R Si This is a base represented by equation (S1).

[0243] In one embodiment, R Si This is a base represented by equation (S2).

[0244] In one embodiment, R Si This is a base represented by formula (S3).

[0245] In one embodiment, R Si This is a base represented by formula (S4).

[0246] In one embodiment, R Si This is a base represented by equation (S5).

[0247] In the above equations (1) and (2), X A The fluoropolyether portion (R) primarily provides water repellency and surface slipperiness. F1 and R F2 ) and the part that provides bonding ability to the substrate (R Si It is understood to be a linker that connects ) and . Therefore, the X A The group may be a single bond or any other group, as long as the compounds represented by formulas (1) and (2) can exist stably.

[0248] In equation (1) above, α is an integer from 1 to 9, and β is an integer from 1 to 9. These α and β are X A It can change depending on the valence of α. The sum of α and β is X A It is the same as the valence of X. For example, X A If is a 10-valent organic group, the sum of α and β is 10, and for example, α can be 9 and β 1, α can be 5 and β 5, or α can be 1 and β 9. Also, X A If it is a divalent organic group, then α and β are 1.

[0249] In equation (2) above, γ is an integer from 1 to 9. γ is X A It can change depending on the valence of X. That is, γ is X A This is the value obtained by subtracting 1 from the valence of [the element].

[0250] X AEach of these is independently a single bond or a 2-10 valent organic group;

[0251] The above X A The 2-10 valent organic group in is preferably a 2-8 valent organic group. In one embodiment, such a 2-10 valent organic group is preferably a 2-4 valent organic group, and more preferably a 2 valent organic group. In another embodiment, such a 2-10 valent organic group is preferably a 3-8 valent organic group, and more preferably a 3-6 valent organic group.

[0252] In one embodiment, X A It is a single-bonded or divalent organic group, where α is 1 and β is 1.

[0253] In one embodiment, X A It is a single-bonded or divalent organic group, and γ is 1.

[0254] In one embodiment, X A is a 3- to 6-valent organic group, with α being 1 and β being 2- to 5.

[0255] In one embodiment, X A γ is a 3- to 6-valent organic group, and γ is 2- to 5.

[0256] In one embodiment, X A It is a trivalent organic group, with α being 1 and β being 2.

[0257] In one embodiment, X A It is a trivalent organic group, and γ is 2.

[0258] X A However, in the case of a single bond or a divalent organic group, formulas (1) and (2) are represented by the following formulas (1') and (2'). [ka]

[0259] In one embodiment, X A It is a single bond.

[0260] In another embodiment, X A It is a divalent organic group.

[0261] In one embodiment, X A For example, a single bond or the following formula: -(R 51 ) p5 -(X 51 ) q5 - [In formula: R 51 This is a single bond, -(CH2) s5 - or o-, m- or p-phenylene group, preferably -(CH2) s5 -and, s5 is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and even more preferably 1 or 2. X 51 is, -(X 52 ) l5 - represents, X 52 These are, independently, -O-, -S-, o-, m- or p-phenylene groups, -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 These are, independently, a phenyl group and a C 1-6 Alkyl alkyl group or C 1-6 Represents an alkoxy group, preferably a phenyl group or C 1-6 It is an alkyl group, more preferably a methyl group, R 54 Each of these is independently a hydrogen atom, a phenyl group, or C 1-6 Represents an alkyl group (preferably a methyl group), Each of m5 is an integer between 1 and 100, preferably between 1 and 20, independently. Each of n5 is an integer between 1 and 20, preferably between 1 and 6, more preferably between 1 and 3. l5 is an integer between 1 and 10, preferably between 1 and 5, more preferably between 1 and 3. p5 is either 0 or 1. q5 is either 0 or 1. Here, at least one of p5 and q5 is 1, and the order of existence of each repeating unit enclosed in parentheses with p5 or q5 is arbitrary. A divalent organic group represented by X is an example. Here, X A (typically X A The hydrogen atom of the fluorine atom, C 1-3 Alkyl and C 1-3 It may be substituted with one or more substituents selected from fluoroalkyl groups. In a preferred embodiment, X A These groups are not substituted by these groups.

[0262] In a preferred embodiment, the above X A These are, independently, -(R 51 ) p5 -(X 51 ) q5 -R 52 - is R 52 This is a single bond, -(CH2) t5 - or o-, m- or p-phenylene group, preferably -(CH2) t5 - is the case. t5 is an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3. Here, R 52 (typically R 52 The hydrogen atom of the fluorine atom, C 1-3 Alkyl and C 1-3 It may be substituted with one or more substituents selected from fluoroalkyl groups. In a preferred embodiment, R 56 These groups are not substituted by these groups.

[0263] Preferably, the above XA Each of them operates independently. single bond, C 1-20 Alkylene group, -R 51 -X 53 -R 52 -, or -X 54 -R 52 - [In the formula, R 51 and R 52 This is synonymous with the 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 has the same meaning as above, u5 represents an integer between 1 and 20, preferably between 2 and 6, more preferably between 2 and 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-, -CONR 54 -(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.) [This represents...] It is possible.

[0264] More preferably, X A Each of them operates independently. single bond, C 1-20 Alkylene group, -(CH2) s5 -X 53 -, -(CH2) s5 -X 53 -(CH2) t5 - -X 54 -, or -X 54 -(CH2) t5 - [where, X 53 , X 54 s5 and t5 have the same meaning as above. That is the case.

[0265] More preferably, the above X A Each of them operates independently. single bond, C 1-20 Alkylene group, -(CH2) s5 -X 53 -(CH2) t5 -, or -X 54 -(CH2) t5 - [In the formula, each symbol has the same meaning as above.] It is possible.

[0266] In a preferred embodiment, the above X A Each of them operates independently. single bond C 1-20 Alkylene group, -(CH2) s5 -X 53 -, or -(CH2) s5 -X 53 -(CH2) t5 - [In the formula, X 53 -O-, -CONR 54 -, or -O-CONR 54 -and, R 54 Each of these is independently a hydrogen atom, a phenyl group, or C 1-6 Represents an alkyl group, s5 is an integer between 1 and 20. t5 is an integer between 1 and 20. It is possible.

[0267] In a preferred embodiment, the above X A Each of them operates independently. -(CH2) s5 -O-(CH2) t5 - -CONR 54 -(CH2) t5 - [In the formula, R 54 Each of these is independently a hydrogen atom, a phenyl group, or C 1-6 Represents an alkyl group, s5 is an integer between 1 and 20. t5 is an integer between 1 and 20. It is possible.

[0268] In one embodiment, the above X A Each of them operates independently. single bond, C 1-20 Alkylene group, -(CH2) s5 -O-(CH2) t5 -, -(CH2) s5 -(Si(R 53 )2O) m5 -Si(R 53 )2-(CH2) t5 -, -(CH2) s5 -O-(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2-(CH2) t5 -, or -(CH2) s5 -O-(CH2) t5 -Si(R 53 )2-(CH2) u5 -Si(R 53 )2-(C v H 2v )- [In the formula, R 53 m5, s5, t5, and u5 have the same meaning as above, and v5 is an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3. That is the case.

[0269] In the above formula, -(C v H 2v )- may be a linear or branched chain, and may be, for example, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)-, or -CH(CH3)CH2-.

[0270] The above X A These are, independently, a fluorine atom and a carbon atom. 1-3 Alkyl and C 1-3 Fluoroalkyl groups (preferably C 1-3 It may be substituted with one or more substituents selected from perfluoroalkyl groups. In one embodiment, X A This is a non-substitution.

[0271] Furthermore, the above X A In each equation, the left side is R F1 or R F2 Combined, the right side is R Si Combine.

[0272] In one embodiment, X A These are, independently, -OC 1-6 It may be a group other than an alkylene group.

[0273] In another embodiment, X A Examples include the following bases: [ka] [ka] [In the formula, R 41 Each of these independently consists of 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 These are, independently, hydrogen atoms and C 1-6 alkyl group or C 1-6 (This represents an alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group.) It is a base selected from, E is -(CH2) n -(n is an integer from 2 to 6), D is the R of the molecular backbone. F1 or R F2 E is bonded to R Si [Combine with...]

[0274] The above X A Specific examples include: single bond, -CH2OCH2-, -CH2O(CH2)2-, -CH2O(CH2)3-, -CH2O(CH2)4-, -CH2O(CH2)5-, -CH2O(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-、 -CH2OCH2CHFCF2OCF2-、 -CH2OCH2CHFCF2OCF2CF2-、 -CH2OCH2CHFCF2OCF2CF2CF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、 -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、 -CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、 -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、 -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、 -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、 -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、 -(CH2)2-Si(CH3)2-(CH2)2-、 -CH2-、 -(CH2)2-、 -(CH2)3-、 -(CH2)4-、 -(CH2)5-, -(CH2)6-, -CO-, -CONH-, -CONH-CH2-, -CONH-(CH2)2-, -CONH-(CH2)3-, -CONH-(CH2)4-, -CONH-(CH2)5-, -CONH-(CH2)6-, -CON(CH3)-CH2-, -CON(CH3)-(CH2)2-, -CON(CH3)-(CH2)3-, -CON(CH3)-(CH2)4-, -CON(CH3)-(CH2)5-, -CON(CH3)-(CH2)6-, -CON(Ph)-CH2- (where Ph represents phenyl), -CON(Ph)-(CH2)2- (wherein Ph means phenyl), -CON(Ph)-(CH2)3-(wherein Ph represents phenyl), -CON(Ph)-(CH2)4-(wherein Ph represents phenyl), -CON(Ph)-(CH2)5-(wherein Ph represents phenyl), -CON(Ph)-(CH2)6-(wherein Ph represents 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) 10 Si(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] These are some examples.

[0275] In yet another embodiment, X A These are independent of each other, and the formula is:-(R 16 ) x1 -(CFR 17 ) y1 -(CH2) z1 This is a base represented by -. In the formula, x1, y1, and z1 are each independent integers between 0 and 10, the sum of x1, y1, and z1 is 1 or greater, and the order of existence of each repeating unit enclosed in parentheses is arbitrary in the formula.

[0276] In the above formula, R 16 These are, independently, an oxygen atom, phenylene, carbasoliene, and -NR. 18 -(In the formula, R 18 R represents a hydrogen atom or an organic group) or a divalent organic group. Preferably, 18 This is an oxygen atom or a divalent polar group.

[0277] The above-mentioned "divalent polar group" is not particularly limited, but includes -C(O)-, -C(=NR 19 )-, and -C(O)NR 19 -(In these formulas, R 19 Examples include (where 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.

[0278] In the above formula, R 17 Each of these is independently a hydrogen atom, a fluorine atom, or a lower fluoroalkyl group, preferably a fluorine atom. The "lower fluoroalkyl group" is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, and even more preferably a trifluoromethyl group.

[0279] In yet another embodiment, X A Examples include the following bases: [ka] [In the formula, R 41 Each of these independently consists of 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 A In the base, any some of T are R of the molecular backbone. F1 or R F2 The following groups that bind to them: -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 These are, independently, hydrogen atoms and C 1-6 alkyl group or C 1-6 This represents an alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group. And some of the other T's are R's of the molecular backbone. Si If bonded, the remaining T, if present, independently consists of a methyl group, a phenyl group, and C. 1-6 It is an alkoxy group, a radical scavenging group, or an ultraviolet absorbing group.

[0280] The radical scavenging group is not particularly limited as long as it can capture radicals generated by light irradiation, but examples include residues of benzophenones, benzotriazoles, benzoic acid esters, phenyl salicylates, crotonic acids, malonic acid esters, organoacrylates, hindered amines, hindered phenols, or triazines.

[0281] The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet light, but examples include residues of benzotriazoles, hydroxybenzophenones, substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, oxanilides, benzoxazinones, and benzoxazoles.

[0282] In a preferred embodiment, preferred radical scavenging groups or ultraviolet absorbing groups are: [ka] These are some examples.

[0283] In this embodiment, X A Each of these can independently be a 3- to 10-valent organic group.

[0284] In yet another embodiment, X A Examples include the following bases: [ka] [In the formula, R 25 , R 26 and R 27 These are each independently 2-6 valent organic groups, R 25 is at least one R F1 Combined with R 26 and R 27 Each of these has at least one R Si [Combine with...]

[0285] In one embodiment, the above R 25 C is a single bond. 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 - is the case. Above, R 57 and R 59 Each of them is independently a single bond, C 1-20 Alkylene group, C 3-20 Cycloalkylene group, or C 5-20 It is an arylene group. 58 These are -O-, -S-, -CO-, -O-CO-, or -COO-.

[0286] In one embodiment, the above R 26 and R 27 Each is independently a hydrocarbon, or a group having at least one atom selected from N, O, and S in the end or main chain of a hydrocarbon, preferably C 1-6 alkyl group, -R 36 -R 37 -R 36 -, -R 36 -CHR 38 2- are examples. Here, R 36 Each of these is 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 R is N, O, or S, preferably N or O. 38 is, -R 45 -R 46 -R 45 -, -R 46 -R 45 -or-R 45 -R 46 - is the case. Here, R 45 Each of these is an alkyl group having 1 to 6 carbon atoms. 46 is N, O, or S, and preferably O.

[0287] In this embodiment, X A Each of these can independently be a 3- to 10-valent organic group.

[0288] In yet another embodiment, X A For example, see below: [ka] [where, X a This refers to a single-bonded or divalent organic group. A group represented by this can be given.

[0289] The above X a X is a single bond or a divalent linking group that is directly bonded to an isocyanuric ring. aPreferably, the group is a divalent group containing a single bond, an alkylene group, or at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond. More preferably, the group is a divalent hydrocarbon group having 1 to 10 carbon atoms containing a single bond, an alkylene group having 1 to 10 carbon atoms, or at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond.

[0290] X a The formula is as follows: -(CX 121 X 122 ) x1 -(X a1 ) y1 -(CX 123 X 124 ) z1 - (In the formula, X 121 ~X 124 These are H, F, OH, or -OSi(OR) respectively, independently. 121 )3(In the formula, three R 121 These are, independently, alkyl groups having 1 to 4 carbon atoms. The above X a1 These are -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, or -NHC(=O)NH- (where the left side of each bond is CX). 121 X 122 It joins to ( ). x1 is an integer between 0 and 10, y1 is either 0 or 1, and z1 is an integer between 1 and 10. A group represented by is even more preferable.

[0291] The above X a1 -O- or -C(=O)O- are preferred.

[0292] The above X a The formula is as follows: -(CF2) m11 -(CH2) m12 -O-(CH2) m13 - (In the formula, m11 is an integer between 1 and 3, m12 is an integer between 1 and 3, and m13 is an integer between 1 and 3.) A base represented by -(CF2) m14 -(CH2) m15 -O-CH2CH(OH)-(CH2) m16 - (In the formula, m14 is an integer between 1 and 3, m15 is an integer between 1 and 3, and m16 is an integer between 1 and 3.) A base represented by -(CF2) m17 -(CH2) m18 - (In the formula, m17 is an integer between 1 and 3, and m18 is an integer between 1 and 3.) A base represented by -(CF2) m19 -(CH2) m20 -O-CH2CH(OSi(OCH3)3)-(CH2) m21 - (In the formula, m19 is an integer between 1 and 3, m20 is an integer between 1 and 3, and m21 is an integer between 1 and 3.) A base represented by, -(CH2) m22 - (In the formula, m22 is an integer between 1 and 3.) A group represented by is particularly preferred.

[0293] The above X a While not particularly limited, specifically, -CH2-, -C2H4-, -C3H6-, -C4H8-, -C4H8-O-CH2-, -CO-O-CH2-CH(OH)-CH2-, -(CF2) n5 -(n5 is an integer between 0 and 4.), -(CF2) n5 -(CH2) m5 -(n5 and m5 are integers between 0 and 4, respectively), -CF2CF2CH2OCH2CH(OH)CH2-, -CF2CF2CH2OCH2CH(OSi(OCH3)3)CH2- These are some examples.

[0294] In this embodiment, XA Each of these can independently be a divalent or trivalent organic group.

[0295] The silane compound represented by formula (1) or formula (2) above is not particularly limited, but 5 × 10 2 ~1 × 10 5 It may have an average molecular weight of 2,000 to 32,000, more preferably 2,500 to 12,000, from the viewpoint of wear resistance. Note that this "average molecular weight" refers to the number average molecular weight, and "average molecular weight" refers to the number average molecular weight. 19 The value shall be measured by 1F-NMR.

[0296] The above-mentioned water-repellent and oil-repellent layer (C) can typically be formed using a surface treatment agent containing the above-mentioned silane compound.

[0297] In one embodiment, such a surface treatment agent may be the silane compound itself.

[0298] In one embodiment, the content of the silane compound may be preferably 0.1 to 50.0% by mass, more preferably 1.0 to 30.0% by mass, even more preferably 5.0 to 25.0% by mass, and particularly preferably 10.0 to 20.0% by mass, relative to the total surface treatment agent.

[0299] In another embodiment, the content of the silane compound may be preferably 0.001 to 30% by mass, more preferably 0.01 to 10% by mass, even more preferably 0.05 to 5% by mass, and particularly preferably 0.05 to 2% by mass, relative to the total surface treatment agent.

[0300] In one embodiment, the surface treatment agent may comprise the composition and at least one compound comprising a condensate formed by the condensation of at least a portion of the silane compound contained in the composition. In other words, the surface treatment agent may contain the silane compound and a condensate formed by the condensation of at least a portion of the silane compound.

[0301] In the above embodiment, the content of the condensate may be preferably 40% by mass or less, more preferably 30% by mass or less, relative to the total amount of the silane compound and the condensate of the silane compound. Here, the content of the condensate can be determined, for example, from the ratio of peak positions and areas in GPC (gel permeation chromatography).

[0302] The above surface treatment agent may further include a solvent, a non-reactive silicone compound that can be understood as a silicone oil (hereinafter referred to as "silicone oil"), an amine compound, alcohols, a catalyst, a surfactant, a polymerization inhibitor, a sensitizer, and the like.

[0303] In one embodiment, the surface treatment agent is R 90 It further contains compounds represented by -OH. R 90 is a monovalent organic group, preferably C 1-20 Alkyl alkyl group or C 3-20 These are alkylene groups, and these groups may be substituted with one or more substituents. Examples of substituents include hydroxyl groups, -OR 91 (Here, R 91 is C 1-10 Alkyl alkyl group, preferably C 1-3 Examples include alkyl groups (for example, a methyl group).

[0304] In one embodiment, the surface treatment agent is R 81 Ure 82 , R 83 n8 C6H 6-n8 , R 84 R 85 R 86 Si-(O-SiR 87 R 88 ) m8 -R 89 , and (OSiR 87 R 88 ) m9 [In the ceremony R 81 ~R 89 Each of these is independently a monovalent organic group with 1 to 10 carbon atoms. m8 is an integer between 1 and 6. m9 is an integer between 3 and 8. n8 is an integer between 0 and 6. It may further contain a solvent selected from the compounds represented by .

[0305] The monovalent organic group having 1 to 10 carbon atoms may be linear, branched, or may even contain a cyclic structure.

[0306] In one embodiment, the monovalent organic group having 1 to 10 carbon atoms may contain an oxygen atom, a nitrogen atom, or a halogen atom.

[0307] In another embodiment, the monovalent organic group having 1 to 10 carbon atoms does not contain a halogen atom.

[0308] In a preferred embodiment, the monovalent organic group having 1 to 10 carbon atoms is a hydrocarbon group which may be substituted with a halogen, preferably an unsubstituted hydrocarbon group.

[0309] In one embodiment, the hydrocarbon group is a straight chain.

[0310] In another embodiment, the hydrocarbon group is a branched chain.

[0311] In another embodiment, the hydrocarbon group includes a cyclic structure.

[0312] In one embodiment, the solvent is R 81 Ure 82 That is the case.

[0313] R 81 and R 82 Each of these is independently preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably C 1-6 Alkyl alkyl group, or C 5-8 It may be a cycloalkyl group.

[0314] In one embodiment, the solvent is R83 n8 C6H 6-n8 That is the case.

[0315] C6H 6-n8 This is an n8 valent benzene ring. That is, R 83 n8 C6H 6-n8 This consists of n8 R 83 This is a benzene substituted with [substance name].

[0316] R 83 Each of these is independently a halogen, or a C which may be substituted with a halogen. 1-6 It can be an alkyl group.

[0317] n8 is preferably an integer between 1 and 3.

[0318] In one embodiment, the solvent is R 84 R 85 R 86 Si-(O-SiR 87 R 88 ) m8 -R 89 That is the case.

[0319] In one embodiment, the solvent is (OSiR 87 R 88 ) m9 (OSiR 87 R 88 ) m9 This involves multiple OSiR 87 R 88 It is a cyclic siloxane formed by the ring-like bonding of units.

[0320] R 84 ~R 89 Each of these is independently a hydrogen atom, or C 1-6 an alkyl group, preferably C 1-6 alkyl groups, more preferably C 1-3 The alkyl group is more preferably a methyl group.

[0321] m8 is preferably an integer between 1 and 6, more preferably an integer between 1 and 5, and even more preferably between 1 and 2.

[0322] m9 is preferably an integer between 3 and 6, more preferably an integer between 3 and 5.

[0323] In one embodiment, the solvent may be, for example, aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, or mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, or 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, or ethyl-2-hydroxybutyl acetate. Esters such as ethyl acetate, ethyl acetate, 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, methylaminoketone, 2-heptanone; ethyl cellosolve, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene Glycol ethers such as 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, iso-propanol, 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, N,N-dimethylacetamide, and N-methylpyrrolidone; ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, and diethylene glycol monomethyl ether; and diethylene glycol monoethyl ether acetate.Polyfluoroaromatic hydrocarbons (e.g., 1,3-bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C6F); 13 CH2CH3 (for example, Asahi Clean® AC-6000 manufactured by Asahi Glass Co., Ltd.), C6F 13H (for example, AsahiClean® AC-2000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeolora® H manufactured by Nippon Zeon Co., Ltd.); fluorinated hydrocarbons such as 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225), and 1,3-bis(trifluoromethyl)benzene; CF3CH2OH, CF3 Fluorine-containing alcohols such as CF2CH2OH and (CF3)2CHOH; hydrofluoroethers (HFE) (e.g., perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec® 7000 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec® 7100 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl ethyl ether (C4F9OC2H5) (e.g., Novec® 7200 manufactured by Sumitomo 3M Co., Ltd.), perfluoro Alkyl perfluoroalkyl ethers such as o-lohexyl methyl ether (C2F5CF(OCH3)C3F7) (e.g., Novec® 7300 manufactured by Sumitomo 3M Limited) (the perfluoroalkyl group and alkyl group may be linear or branched), or CF3CH2OCF2CHF2 (e.g., Asahiclean® AE-3000 manufactured by Asahi Glass Co., Ltd.), hydrofluoroolefins; CF3CH=CHCl (e.g., CELEFIN® 1233Z manufactured by Central Glass Co., Ltd.) Examples include ethers such as ), CHF2CF=CHCl (for example, AMOLEA® AS-300 manufactured by Asahi Glass Co., Ltd.), and cyclopentyl methyl ether; siloxanes such as hexamethyldisiloxane, hexaethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, octamethylcyclopentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and tetradecamethylhexasiloxane; and dimethyl sulfoxides. Alternatively, mixed solvents of two or more of these are also possible.Among these, aliphatic hydrocarbons, aromatic hydrocarbons, esters, glycol ethers, alcohols, ether alcohols, and siloxanes are preferred. For example, hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirits, benzene, toluene, xylene, naphthalene, 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, ethyl-2-hydroxybutyrate, ethyl acetate acetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, 2- Ethyl propylene glycol monomethyl ether hydroxyisobutyrate, propylene glycol monoethyl ether, propylene glycol monobutyl ether, methanol, ethanol, iso-propanol, n-butanol, isobutanol, tert-butanol, sec-butanol, diethylene glycol monomethyl ether, hexamethyldisiloxane, hexaethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, octamethylcyclotetrasiloxane, and octamethylcyclopentasiloxane are preferred.

[0324] The silicone oil is not particularly limited, but for example, the following general formula (3a): R 101a -(SiR 103a 2-0) a1 -SiR 103a 2-R 101a ...(3a) [In formula: R 101a Each of these is independently a hydrogen atom or a hydrocarbon group. R 103a Each of these is independently a hydrogen atom or a hydrocarbon group. a1 is between 2 and 3000. Examples of compounds represented by [the formula shown] are given.

[0325] The above R 103a Each of these is independently either a hydrogen atom or a hydrocarbon group. Such hydrocarbon groups may be substituted.

[0326] R 103a Each of these is independently preferably an unsubstituted hydrocarbon group or a hydrocarbon group substituted with a halogen atom.

[0327] R 103a Each of these C atoms may be independently substituted, preferably with a halogen atom. 1-6 Alkyl group or aryl group, more preferably C 1-6 It is an alkyl group or an aryl group.

[0328] C above 1-6 The alkyl group may be linear or branched, but linear is preferred. C 1-6 The alkyl group is preferably C 1-3 An alkyl group, more preferably a methyl group.

[0329] The above aryl group is preferably a phenyl group.

[0330] In one embodiment, R 103a Each of them is independent of C 1-6 Alkyl alkyl group, preferably C 1-3 An alkyl group, more preferably a methyl group.

[0331] In another embodiment, R 103a This is a phenyl group.

[0332] In another embodiment, R 103a This is a methyl group or a phenyl group, preferably a methyl group.

[0333] The above R 101a Each of these is independently a hydrogen atom or a hydrocarbon group, and the above R 3a It is synonymous with [the above].

[0334] R 101a Each of these C atoms may be independently substituted, preferably with a halogen atom. 1-6 Alkyl group or aryl group, more preferably C 1-6 It is an alkyl group or an aryl group.

[0335] In one embodiment, R 101a Each of them is independent of C 1-6 Alkyl alkyl group, preferably C 1-3 An alkyl group, more preferably a methyl group.

[0336] In another embodiment, R 101a This is a phenyl group.

[0337] In another embodiment, R 101a This is a methyl group or a phenyl group, preferably a methyl group.

[0338] The above a1 is between 2 and 1500. a1 is preferably 5 or more, more preferably 10 or more, even more preferably 15 or more, for example 30 or more, or 50 or more. a1 is preferably 1000 or less, more preferably 500 or less, even more preferably 200 or less, even more preferably 150 or less, for example 100 or less, or 80 or less.

[0339] a1 may preferably be 5 to 1000, more preferably 10 to 500, even more preferably 15 to 200, and even more preferably 15 to 150.

[0340] Other silicone oils include the following (3b): R 101a -R SO2 -R 103a ...(3b) [In formula: R 101a Each of these is independently a hydrocarbon group, R 103a Each of these is independently a hydrocarbon group, R SO2 is, -R S-SiR 5 2- and R S and R 5 This is synonymous with the above. Examples of compounds represented by [the formula shown] are given.

[0341] The above-mentioned silicone oil may have an average molecular weight of 500 to 1,000,000, preferably 1,000 to 100,000. The molecular weight of the silicone oil can be measured using GPC.

[0342] Examples of the above silicone oils include -(SiR 3a 2-0) a1 A linear or cyclic silicone oil with a1 of -30 or less may be used. Linear silicone oils may be so-called straight silicone oils and modified silicone oils. 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. An example of a cyclic silicone oil is cyclic dimethylsiloxane oil.

[0343] The above-mentioned silicone oil may be present in the above-mentioned surface treatment agent in an amount of, for example, 0 to 50% by mass, preferably 0.001 to 30% by mass, and more preferably 0.1 to 5% by mass.

[0344] In the above surface treatment agent, the silicone oil may be included in an amount of, for example, 0 to 300 parts by mass, preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, and even more preferably 0 to 10 parts by mass, based on 100 parts by mass of the total of the compounds contained in the composition of the present disclosure (the sum of the two or more compounds if there are two or more, and the same applies hereinafter).

[0345] Silicone oil contributes to improving the surface lubricity of the surface-treated layer.

[0346] Examples of the alcohols mentioned above include methanol, ethanol, iso-propanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octyl alcohol, 3-methyl-3-methoxybutanol, and tert-amyl alcohol. Adding these alcohols to the composition improves the stability of the composition.

[0347] Examples of catalysts include acids (e.g., acetic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, sulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, etc.), bases (e.g., sodium hydroxide, potassium hydroxide, ammonia, triethylamine, diethylamine, etc.), transition metals (e.g., Ti, Ni, Sn, Zr, Al, B, Si, Ta, Nb, Mo, W, Cr, Hf, V, etc.), sulfur-containing compounds having lone pairs of electrons in their molecular structure, or nitrogen-containing compounds (e.g., sulfoxide compounds, aliphatic amine compounds, aromatic amine compounds, phosphate amide compounds, amide compounds, urea compounds, etc.).

[0348] Examples of the above-mentioned aliphatic amine compounds include diethylamine and triethylamine. Examples of the above-mentioned aromatic amine compounds include aniline and pyridine.

[0349] In a preferred embodiment, the transition metal is included as a transition metal compound represented by the formula MR (wherein M is a transition metal atom and R is a hydrolyzable group). By making the transition metal compound a compound in which a transition metal and a hydrolyzable group are bonded, transition metal atoms can be more efficiently incorporated into the surface treatment layer, further improving the friction durability and chemical resistance of the surface treatment layer.

[0350] The above-mentioned hydrolyzable group refers to a group that can undergo hydrolysis, similar to the hydrolyzable group relating to the above-mentioned compound; that is, a group that can be removed from the transition metal atom by hydrolysis. Examples of hydrolyzable groups include -OR m , -OCOR m , -ON=CRm 2. -NR m 2, -NHR m , -NCO, halogen (in these formulas, R m C is either substituted or non-substituted. 1-4 Examples include (showing an alkyl group).

[0351] In a preferred embodiment, the hydrolyzable group is -OR m The group is preferably methoxy or ethoxy. By using an alkoxy group as the hydrolyzable group, transition metal atoms can be more efficiently incorporated into the surface treatment layer, further improving the friction durability and chemical resistance of the surface treatment layer.

[0352] In one embodiment, the hydrolyzable group may be the same as the hydrolyzable group contained in the compound described above. By making the hydrolyzable group in the compound and the transition metal compound the same, the effect can be reduced even if such hydrolyzable groups are exchanged with each other.

[0353] In another embodiment, the hydrolyzable group may be different from the hydrolyzable group contained in the compound described above. By making the hydrolyzable group in the compound different from that in the transition metal compound, the reactivity of hydrolysis can be controlled.

[0354] In one embodiment, the hydrolyzable group and the hydrolyzable group contained in the compound may be interchangeable in the composition.

[0355] In a preferred embodiment, the transition metal compound is Ta(OR m )5(wherein, R m C is either substituted or non-substituted. 1-4 It is an alkyl group. Preferably Ta(OCH2CH3)5, or Si(OR m ) 1-m1 R m’ m1 (In the formula, R m C is either substituted or non-substituted. 1-4 It is an alkyl group, R m’C 1-4 It is an alkyl group, and m1 is 0 or 1. Preferably, it may be tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetraisopropoxysilane, dimethyldiethoxysilane, or dimethyldimethoxysilane.

[0356] The catalyst may be present in the entire surface treatment agent (coating liquid) at a concentration of, for example, 0.0002% by mass or more. Preferably, the catalyst is present at a concentration of 0.02% by mass or more, and more preferably at a concentration of 0.04% by mass or more, relative to the entire surface treatment agent (coating liquid). The catalyst may be present at a concentration of, for example, 10% by mass or less, and particularly at a concentration of 1% by mass or less, relative to the entire surface treatment agent (coating liquid). The surface treatment agent, when the catalyst is present at the above concentrations, can contribute to the formation of a surface treatment layer with better durability.

[0357] The content of the catalyst is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and particularly preferably 0 to 1% by mass, relative to the compounds contained in the composition of the present disclosure.

[0358] The catalyst promotes the hydrolysis and dehydration condensation of the compounds contained in the composition of the disclosure, thereby promoting the formation of the layer formed by the composition of the disclosure.

[0359] Other components besides those listed above include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and methyltriacetoxysilane.

[0360] In addition to the components mentioned above, the surface treatment agent may contain trace amounts of impurities such as Pt, Rh, Ru, 1,3-divinyltetramethyldisiloxane, triphenylphosphine, NaCl, KCl, and silane condensates.

[0361] In one embodiment, the surface treatment agent is for a dry coating method, preferably for vacuum deposition.

[0362] In one embodiment, the surface treatment agent is for a wet coating method, preferably an immersion coating.

[0363] The above surface treatment agent can be impregnated into porous materials, such as porous ceramic materials, or metal fibers, such as steel wool compressed into a cotton-like form, to form pellets. These pellets can be used, for example, in vacuum deposition.

[0364] The compounds of this disclosure are preferably used as surface treatment agents or as components of surface treatment agents.

[0365] The product can be manufactured by forming the silicon oxide layer (B) on the surface of the substrate (A), further forming a water-repellent and oil-repellent layer (C) on the surface of the silicon oxide layer (B) on the surface of the silicon oxide layer (B), and then post-treating this layer as needed to form the water-repellent and oil-repellent layer (C).

[0366] The formation of the water-repellent, permeable layer (C) using the above-mentioned surface treatment agent can be achieved by applying the surface treatment agent to the surface of the silicon oxide layer (B) so as to cover the surface. The coating method is not particularly limited. For example, wet coating and dry coating methods can be used.

[0367] Examples of wet coating methods include immersion coating, spin coating, flow coating, spray coating, roll coating, gravure coating, wipe coating, squeegee coating, die coating, inkjet, cast coating, Langmuir-Bludget method, and similar methods.

[0368] 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 beams, high-frequency heating using microwaves, ion beams, and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.

[0369] Furthermore, coating using the atmospheric pressure plasma method is also possible.

[0370] When using a wet coating method, the surface treatment agents of the present disclosure may be diluted with a solvent before being applied to the substrate surface. From the viewpoint of the stability of the composition of the present disclosure and the volatility of the solvent, the following solvents are preferably used: 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, and carboxymethyl acetate. Esters such as tol, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methylaminoketone, and 2-heptanone; ethyl cellosol, methyl cellosol Glycol ethers such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene 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, iso-propanol, 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, N,N-dimethylacetamide, and N-methylpyrrolidone;Ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, and diethylene glycol monomethyl ether; diethylene glycol monoethyl ether acetate; polyfluoroaromatic hydrocarbons (e.g., 1,3-bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C6F); 13 CH2CH3 (for example, Asahi Clean® AC-6000 manufactured by Asahi Glass Co., Ltd.), C6F 13H (for example, AsahiClean® AC-2000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeolora® H manufactured by Nippon Zeon Co., Ltd.); fluorinated hydrocarbons such as 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225), and 1,3-bis(trifluoromethyl)benzene; CF3CH2OH, C Fluorine-containing alcohols such as F3CF2CH2OH and (CF3)2CHOH; hydrofluoroethers (HFE) (e.g., perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec® 7000 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec® 7100 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl ethyl ether (C4F9OC2H5) (e.g., Novec® 7200 manufactured by Sumitomo 3M Co., Ltd.), Alkyl perfluoroalkyl ethers such as perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (e.g., Novec® 7300 manufactured by Sumitomo 3M Limited) (the perfluoroalkyl group and alkyl group may be linear or branched), or CF3CH2OCF2CHF2 (e.g., AsahiClean® AE-3000 manufactured by Asahi Glass Co., Ltd.), hydrofluoroolefins; CF3CH=CHCl (e.g., CELEFIN® manufactured by Central Glass Co., Ltd.) Examples include ethers such as 1233Z), CHF2CF=CHCl (for example, AMOLEA® AS-300 manufactured by Asahi Glass Co., Ltd.), and cyclopentyl methyl ether; siloxanes such as hexamethyldisiloxane, hexaethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, octamethylcyclopentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and tetradecamethylhexasiloxane; dimethyl sulfoxide, etc. Or mixed solvents of two or more of these.Among these, aliphatic hydrocarbons, aromatic hydrocarbons, esters, glycol ethers, alcohols, ether alcohols, and siloxanes are preferred. For example, hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirits, benzene, toluene, xylene, naphthalene, 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, ethyl-2-hydroxybutyrate, ethyl acetate acetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, 2- Ethyl propylene glycol monomethyl ether hydroxyisobutyrate, propylene glycol monoethyl ether, propylene glycol monobutyl ether, methanol, ethanol, iso-propanol, n-butanol, isobutanol, tert-butanol, sec-butanol, diethylene glycol monomethyl ether, hexamethyldisiloxane, hexaethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, octamethylcyclotetrasiloxane, and octamethylcyclopentasiloxane are preferred.

[0371] In one aspect, when using the wet coating method, the solvent is, for example, R 90 Compounds represented by -OH can be used. 90 is a monovalent organic group, preferably C 1-20 Alkyl alkyl group or C 3-20 These are alkylene groups, and these groups may be substituted with one or more substituents. Examples of substituents include hydroxyl groups, -OR 91 (Here, R 91 is C 1-10 Alkyl alkyl group, preferably C 1-3 Examples include alkyl groups (for example, a methyl group).

[0372] When using the dry coating method, the above surface treatment agent may be applied to the dry coating method as is, or it may be diluted with the above solvent before being applied to the dry coating method.

[0373] The layer formation of the surface treatment agent is preferably carried out so that the surface treatment agent exists in the layer together with a catalyst for hydrolysis and dehydration condensation. For convenience, in the case of the wet coating method, the catalyst may be added to the diluted solution of the surface treatment agent immediately after diluting it with a solvent and applying it to the substrate surface. In the case of the dry coating method, the surface treatment agent with the catalyst added may be directly vapor-deposited (usually by vacuum deposition), or a pellet-like material impregnated with the catalyst-added surface treatment agent of the disclosure, such as iron or copper, may be used for vapor deposition (usually by vacuum deposition).

[0374] Any suitable acid or base, transition metals (e.g., Ti, Ni, Sn, Zr, Al, B, etc.), sulfur-containing compounds having lone pairs of electrons in their molecular structure, or nitrogen-containing compounds (e.g., sulfoxide compounds, aliphatic amine compounds, aromatic amine compounds, phosphate amide compounds, amide compounds, urea compounds, etc.) can be used as catalysts. Examples of acid catalysts include acetic acid, formic acid, trifluoroacetic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid. Examples of base catalysts include ammonia, sodium hydroxide, potassium hydroxide, and organic amines such as triethylamine and diethylamine. Examples of transition metals, aliphatic amine compounds, and aromatic amine compounds are the same as those mentioned above.

[0375] The water- and oil-repellent layer (C) contained in the article of this disclosure may have high durability. In addition to high durability, the water- and oil-repellent layer (C) may also have water repellency, oil repellency, stain resistance (e.g., preventing the adhesion of dirt such as fingerprints), waterproofness (preventing water from entering electronic components, etc.), surface slipperiness (or lubricity, e.g., ease of wiping away dirt such as fingerprints and excellent tactile feel to the fingers), and chemical resistance, and may be suitably used as a functional thin film.

[0376] Accordingly, this disclosure also relates to optical materials having the above-mentioned water-repellent and oil-repellent layer (C) as the outermost layer.

[0377] As optical materials, a wide variety of optical materials are preferred, in addition to optical materials related to displays, as exemplified below: for example, displays such as cathode ray tubes (CRTs; e.g., PC monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFDs), field emission displays (FEDs), or protective plates for such displays, or materials on which an anti-reflective coating has been applied to their surface.

[0378] The articles of this disclosure may be optical components, but are not limited to these. Examples of optical components include: lenses such as those in eyeglasses; front protective plates, anti-reflective 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 for optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; optical fibers; and display surfaces for watches.

[0379] Furthermore, the articles of this disclosure may be medical devices or medical materials. Also, articles having layers obtained by this disclosure may be automotive interior and exterior components. Examples of exterior components include: windows, light covers, and exterior camera covers. Examples of interior components include: instrument panel covers, navigation system touch panels, and decorative interior components.

[0380] The thickness of the water-repellent and oil-repellent layer (C) is not particularly limited. In the case of optical components, the thickness of the layer may be in the range of, for example, 1 to 50 nm, preferably 1 to 30 nm, and more preferably 1 to 15 nm, from the viewpoint of optical performance, abrasion resistance, and antifouling properties.

[0381] For X-ray photoelectron spectroscopy (XPS) analysis to measure the atomic composition and constituent atom ratios of the water- and oil-repellent layer (C), the ULVAC-PHI PHI5000VersaProbeII can be used. XPS analysis conditions include a 25W monochromatic AlKα X-ray source, a 1400μm × 300μm photoelectron detection area, a photoelectron detection angle in the range of 20 to 90 degrees (e.g., 20, 45, 90 degrees), and a pass energy of 23.5eV. For sputtering, gas cluster ion beams or Ar ions can be used. Using the above apparatus and measurement conditions, the peak areas of C1s, O1s, and Si2p can be observed, and the atomic ratios of carbon, oxygen, and silicon can be calculated to determine the composition of the water- and oil-repellent layer (C) and the silicon oxide layer (B).

[0382] Furthermore, depth analysis can also be performed. For XPS analysis, the measurement conditions include using a monochromatic AlKα X-ray source at 25W, a photoelectron detection area of ​​1400 μm × 300 μm, a photoelectron detection angle in the range of 20 to 90 degrees (e.g., 20 degrees, 45 degrees, 90 degrees), and a pass energy of 23.5 eV. Sputter ions such as Ar ions, gas cluster ions, and C60 ions can be used. Sputtering can also be used to etch 1 to 100 nm and obtain the composition of the coating film at each etching depth.

[0383] By adjusting the photoelectron detection angle in the XPS analysis described above, the detection depth can be adjusted as needed. For example, by setting a shallow angle close to 20 degrees, the detection depth can be set to about 3 nm, while by setting a deep angle close to 90 degrees, the detection depth can be set to about 10-something nm.

[0384] The compounds, compositions, and articles of this disclosure have been described in detail above. However, the compounds, compositions, and articles of this disclosure are not limited to those exemplified above. [Examples]

[0385] The present invention will be further described in detail by the following examples, but the present invention is not limited thereto.

[0386] (Preparation of Binder Solution 1) 1.40 g of tetraethoxysilane and 3.18 g of ethanol were added to a 30 mL flask and stirred at room temperature for 30 minutes. 2.42 g of 0.01 M hydrochloric acid and 5.1 mg of sodium chloride were added to the resulting mixture and stirred at 50°C for 1 hour. 0.25 g of the resulting reaction solution and 4.75 g of ethanol were mixed in a 10 mL screw-bottle to prepare binder solution 1.

[0387] (Preparation of Binder Solution 2) 0.60 g of tetraethoxysilane and 1.36 g of ethanol were added to a 10 mL flask and stirred at room temperature for 30 minutes. To the resulting mixture, 1.04 g of 1 M p-toluenesulfonic acid aqueous solution and 87.7 mg of sodium p-toluenesulfonate were added and stirred at 50°C for 1 hour. 0.25 g of the resulting reaction solution and 4.75 g of ethanol were mixed in a 10 mL screw-bottle to prepare binder solution 2.

[0388] (Preparation of Binder Solution 3) 1.00 g of tetraethoxysilane and 2.26 g of ethanol were added to a 10 mL flask and stirred at room temperature for 30 minutes. To the resulting mixture, 1.73 g of 0.01 M aqueous nitric acid solution and 64.0 mg of sodium nitrate were added and stirred at 50°C for 1 hour. 0.25 g of the resulting reaction solution and 4.75 g of ethanol were mixed in a 10 mL screw-bottle to prepare binder solution 3.

[0389] (Preparation of Binder Solution 4) 0.40 g of tetraethoxysilane and 0.91 g of ethanol were added to a 10 mL flask and stirred at room temperature for 30 minutes. To the resulting mixture, 0.69 g of 0.01 M hydrochloric acid and 44.0 mg of sodium chloride were added and stirred at 50°C for 1 hour. 0.25 g of the resulting reaction solution, 2.75 g of ethanol, and 2.00 g of deionized water were mixed in a 10 mL screw-bottle to prepare binder solution 4.

[0390] (Preparation of Binder Solution 5) 0.20 g of tetraethoxysilane and 0.46 g of ethanol were added to a 10 mL flask and stirred at room temperature for 30 minutes. To the resulting mixture, 0.35 g of 0.01 M hydrochloric acid and salt were added. change 44.0 mg of sodium was added and the mixture was stirred at 50°C for 1 hour. 0.25 g of the resulting reaction solution, 2.75 g of ethanol, and 2.00 g of deionized water were mixed in a 10 mL screw-bottle to prepare binder solution 5.

[0391] (Preparation of binder solution 6) 7.0 g of tetraethoxysilane and 15.9 g of ethanol were added to a 100 mL flask and stirred at room temperature for 30 minutes. To the resulting mixture, 12.1 g of 0.01 M hydrochloric acid and salt were added. change 2.6 mg of sodium was added and the mixture was stirred at 50°C for 1 hour. 0.25 g of the resulting reaction solution and 4.75 g of ethanol were mixed in a 10 mL screw-cap bottle to prepare binder solution 6.

[0392] (Preparation of Binder Solution 7) 7.00 g of tetraethoxysilane and 15.6 g of ethanol were added to a 100 mL flask and stirred at room temperature for 30 minutes. To the resulting mixture, 12.1 g of 0.01 M aqueous nitric acid solution and 3.7 mg of sodium nitrate were added and stirred at 50°C for 1 hour. 0.25 g of the resulting reaction solution and 4.75 g of ethanol were mixed in a 10 mL screw-bottle to prepare binder solution 7.

[0393] The compounds used in the examples and comparative examples are as follows: (Compound A) CF3O(CF2CF2O) 15 (CF2O) 16 CF2CH2OCH2CH2CH2Si[CH2CH2CH2Si(OCH3)3]3 (Compound B) CF3CF2CF2O(CF2CF2CF2O) 20 CF2CF2CONHCH2C[CH2CH2CH2Si(OCH3)3]3 (Compound C) CF3O(CF2CF2OCF2CF2CF2CF2O) 13 CF2CF2OCF2CF2CF2C(O)NHCH2C[CH2CH2CH2Si(OCH3)3]3

[0394] (Preparation of surface treatment agents A to C) The compounds A to C described above were each diluted to obtain a 0.5 wt% Novec 7200 (product name, manufactured by 3M) solution to obtain surface treatment agents A to C.

[0395] (Example 1) <Formation of the binder layer> Chemically strengthened glass (Corning Gorilla Glass, 0.7 mm thick) was dry-cleaned with UV / O3 treatment for 10 minutes, and then treated with binder solution 1 by spin-coating at 3000 rpm for 30 seconds. Subsequently, binder layer 1 was obtained by heat treatment in an oven at 150°C for 2 hours.

[0396] <Formation of surface treatment layer> The chemically strengthened glass with the binder layer obtained above was dry-cleaned by UV / O3 treatment for 10 minutes, and then treated with surface treatment agent A by spin-coating at 3000 rpm for 30 seconds. Subsequently, the surface treatment layer was obtained by heating in an oven at 150°C for 30 minutes.

[0397] (Examples 2-15, Comparative Examples 1-2) Examples 2-15 and Comparative Examples 1-2 obtained surface-treated layers with a binder layer using the same procedure as in Example 1, except that the binder solution and surface treatment agent were changed to the combinations shown in Table 1.

[0398] (Comparative Examples 3-5) Silicon oxide (SiO2(C) manufactured by Canon Optron) was placed as a deposition limit on a molybdenum boat inside the vacuum deposition apparatus. The above chemically strengthened glass was placed inside the vacuum deposition apparatus, and silicon oxide was vacuum deposited onto the ion-cleaned surface to obtain a binder layer 8.

[0399] A surface treatment layer with a binder layer was obtained by applying surface treatment agents 1 to 3 to the obtained binder layer 8 using the same procedure as in Example 1.

[0400] (Surface analysis TOF-SIMS, alkali metal analysis) In the silicon oxide layer, the average sodium concentration in the region between 0.1 nm and 0.3 nm in depth from the surface in contact with the water-repellent and oil-repellent layer was determined using a time-of-flight secondary ion mass spectrometer (TOF-SIMS) according to the following procedure.

[0401] (I) First, a standard sample for determining sodium concentration was prepared. A quartz glass substrate with the same composition as the silicon oxide layer to be evaluated was prepared, and sodium was ion-implanted into this substrate to create the standard sample. A medium-current ion implanter (ULVAC IMX-3500RS) was used for ion implantation, with an energy of 110 keV and a sodium implantation rate of 6.0 × 10⁻⁶. 14 ions / cm 2 That's what I decided.

[0402] (II) Next, the silicon dioxide-coated substrate to be evaluated and the standard sample prepared in (I) are simultaneously transported into the TOF-SIMS instrument, and TOF-SIMS depth profiling analysis is performed sequentially by ion sputtering, and the sputtering time (seconds, horizontal axis) and 23 Na + and 28 Si + A profile was obtained showing the intensity (counts, vertical axis).

[0403] Next, from the profile of the substrate prepared in (I), the sputtering rate (nm / second) and count number of sputtered ions are converted to a coefficient (atoms / (counts·cm) for the amount of sodium per unit volume. 3 )) was calculated. The TOF-SIMS analysis conditions used in this study are as follows: Primary ion species: Bi 3+ Primary ion acceleration voltage: 25 keV Primary ion current value: 1 pA (at 10 kHz) Primary ion cluster size: 100 x 100 μm 2 Primary ion punching: Yes Cycle time: 100us Pixel count: 128 x 128 pixels Sputter ion species: C 60 ++ Sputtering acceleration voltage: 10 keV Sputtering current: 1nA (at 10kHz) Sputter ion raster size: 1000 x 1000 μm 2 Sputtering time per pass: 2 seconds Vacuum degree: 5.0×10 -6 mbar (without oxygen flow into the device) Neutralizing gun: None

[0404] (III) Finally, from the depth profile of the sodium concentration of silicon dioxide obtained in (II), the average sodium concentration in the silicon dioxide layer was calculated in the region between 0.1 nm and 0.3 nm in depth from the surface in contact with the water-repellent and oil-repellent layer. Three points were plotted in the region between 0.1 nm and 0.3 nm in depth. The average sodium concentration was calculated as the average of these three points. When measurements are performed under the above conditions, three plots may exist in the region between 0.1 nm and 0.3 nm in depth from the surface in contact with the oil-repellent layer.

[0405] In this example, prior to TOF-SIMS depth profiling by ion sputtering, the silicon dioxide-coated substrate was dry-cleaned by UV / O3 treatment for 10 minutes. Table 1 shows the results of calculating the average sodium concentration in the silicon dioxide layer in the region between 0.1 nm and 0.3 nm in depth from the surface in contact with the water-repellent and oil-repellent layer.

[0406] Prior to TOF-SIMS depth profiling by ion sputtering, it is desirable that the silicon oxide layer be exposed. That is, if a water- and oil-repellent layer is present on the surface of the silicon oxide layer, or if surface contamination is clearly advanced, it is preferable to remove them. Removal methods include oxygen plasma treatment and UV / O3 treatment. Depending on the thickness of the water- and oil-repellent layer and the degree of surface contamination, it is better to perform both.

[0407] (Surface analysis TOF-SIMS analysis) In the silicon oxide layer, Cl in the region where the depth from the surface in contact with the water-repellent and oil-repellent layer is 0.1 nm or more and 0.3 nm or less. - , SO3 - NO3 - SO4 2- , PO3 - and PO4 3- The presence or absence of detection was analyzed using a time-of-flight secondary ion mass spectrometer (TOF-SIMS) according to the following procedure.

[0408] (I) First, the silicon dioxide-coated substrate to be evaluated and the aforementioned standard sample for sodium concentration quantification are simultaneously transported into the TOF-SIMS instrument, and TOF-SIMS depth profiling analysis is performed sequentially by ion sputtering, and the sputtering time (seconds, horizontal axis) and Cl - , SO3 - NO3 - SO4 2- , PO3 - and PO4 3- SiO2 - and Si - A profile was obtained showing the intensity (counts, vertical axis). Next, the sputtering rate (nm / second) of sputtered ions was calculated from the substrate profile of the standard sample. The TOF-SIMS analysis conditions used in this study are as follows: Primary ion species: Bi 3+ Primary ion acceleration voltage: 25 keV Primary ion current value: 1 pA (at 10 kHz) Primary ion cluster size: 100 x 100 μm 2 Primary ion punching: Yes Cycle time: 100us Pixel count: 128 x 128 pixels Sputter ion species: C 60 ++ Sputtering acceleration voltage: 10 keV Sputtering current: 1nA (at 10kHz) Sputter ion raster size: 300 x 300 μm 2 Sputtering time per pass: 4 seconds Vacuum degree: 5.0×10 -6 mbar (without oxygen flow into the device) Neutralizing gun: None

[0409] (II) Next, from the depth profile of silicon oxide obtained in (I), in the silicon oxide layer, in the region where the depth from the surface in contact with the water-repellent and oil-repellent layer is 0.1 nm or more and 0.3 nm or less, Cl - , SO3 - NO3 - SO4 2- , PO3 - and PO4 3- SiO2 - and Si - The average count for each of the above six types and the average total count were calculated. Note that there were 3 points plotted in the region between 0.1 nm and 0.3 nm. - , SO3 - NO3 - SO4 2- , PO3 - , PO4 3- SiO2 - and Si - Furthermore, the average value of the total ion count was calculated as the average of these three points. When measurements are taken under the above conditions, three plot points may exist in the region where the depth from the surface in contact with the oil-repellent layer is between 0.1 nm and 0.3 nm.

[0410] In the silicon oxide layer, in the region where the depth from the surface in contact with the water-repellent and oil-repellent layer is 0.1 nm or more and 0.3 nm or less, (Cl - , SO3 - NO3 - SO4 2- , PO3 - , PO4 3- SiO2 - or Si - Calculate the fraction ) / (total ion count), and if it is 1.0% or more, Cl - , SO3 - NO3 - SO4 2- , PO3 - , PO4 3- SiO2 - or Si - It was determined that (NO3) was detected. For example, the silicon oxide layer used in Example 1 was (NO3 - The total ion count was 3.7%, and NO3 - It was reported that Cl was detected in the silicon oxide layer in a region where the depth from the surface in contact with the water-repellent and oil-repellent layer is between 0.1 nm and 0.3 nm. - , SO3 - NO3 - SO4 2- , PO3 - , PO4 3- SiO2 - or Si - The detection results are shown in Table 1.

[0411] [Table 1]

[0412] (Abrasion resistance evaluation) <Initial Evaluation> For the initial evaluation (zero wear cycles), the static contact angle of water was measured after the surface treatment layer was formed and any excess material on the surface was wiped off. The contact angle was measured using a fully automatic contact angle meter, DropMaster700 (Kyowa Interface Science Co., Ltd.), in a 25°C environment. Specifically, the substrate with the surface treatment layer to be measured was placed horizontally, water was dropped onto its surface from a microsyringe, and the static contact angle was measured by capturing a still image with a video microscope one second after dropping. The static contact angle was measured at five different points on the surface treatment layer of the substrate, and the average value was calculated. If the value was 100° or higher, it was marked as ○, and if it was less than 100°, it was marked as ×.

[0413] <Evaluation after abrasion resistance test> The friction element described below was brought into contact with the formed surface treatment layer, a load of 5N was applied, and the friction element was moved back and forth at a speed of 40 mm / second while the load was applied. When the number of friction cycles reached 10,000, the static contact angle of water was measured, and a value of ○ was used if it was 100° or more, and a × if it was less than 100°. The results are shown in Table 2.

[0414] ·Friction element The surface of the silicone rubber processed product shown below was covered with cotton soaked in artificial sweat of the composition shown below, and this was used as a friction element. Composition of artificial sweat: Anhydrous disodium hydrogen phosphate: 2g Sodium chloride: 20g 85% Lactic Acid: 2g Histidine hydrochloride: 5g Distilled water: 1 kg Silicone rubber processed products: This is a silicone rubber stopper SR-51 manufactured by Tigers Polymer, processed into a cylindrical shape with a diameter of 1 cm and a thickness of 1 cm.

[0415] [Table 2]

Claims

1. Substrate (A), Water-repellent and oil-repellent layer (C), Displaced between the substrate (A) and the water-repellent and oil-repellent layer (C), alkali metal atoms and Cl － NO ３ － and SO ３ A silicon oxide layer (B) comprising one or more selected from the group consisting of - In the silicon oxide layer (B), in a region with a depth of 0.1 to 0.3 nm from the surface in contact with the water-repellent and oil-repellent layer (C), the average concentration of alkali metal atoms is 1.4 × 10⁻¹⁶. １８ atoms / cm ３ The above 2.0 x 10 １９ atoms / cm ３ It is less than, The thickness of the silicon oxide layer (B) is 15 nm or less. The silicon oxide layer (B) is formed from a binder composition, The binder composition comprises a silicon dioxide precursor, an acid, and an alkali metal salt. The alkali metal salt comprises one or more selected from chloride salts, nitrates, and sulfates. The water- and oil-repellent layer (C) is formed using a surface treatment agent containing a silane compound having Si atoms to which hydroxyl groups or hydrolyzable groups are bonded. The silane compound is an article having a fluorine atom.

2. The article according to claim 1, wherein the alkali metal atom includes a sodium atom.

3. The article according to claim 1, wherein the silicon oxide layer (B) comprises one or more selected from condensates of silicate compounds and hydrolysates of alkoxysilanes.

4. The silicon oxide layer (B) is formed from a liquid binder composition. The article according to claim 1, wherein the liquid binder composition comprises a silicon dioxide precursor, an acid, an alkali metal salt, and a solvent.

5. The article according to claim 1, wherein the silicon dioxide precursor comprises one or more selected from silicic acid compounds, condensates of silicic acid compounds, alkoxysilanes, and hydrolysis condensates of alkoxysilanes.

6. The silane compound in the water-repellent and oil-repellent layer (C) is of the following formula (1) or (2): 【Chemistry 1】 [In the formula: R Ｆ１ is, independently of each other, Rf １ -R Ｆ -O ｑ -; R Ｆ２ is, -Rf ２ ｐ -R Ｆ -O ｑ - and; Rf １ Each of these C atoms may be independently substituted with one or more fluorine atoms. １－１６ It is an alkyl group; Rf ２ C may be substituted with one or more fluorine atoms. １－６ It is an alkylene group; R Ｆ Each of these is independently a divalent fluoropolyether group; p is either 0 or 1; q is either 0 or 1, independently of each other; R Ｓｉ Each of these is independently a monovalent group containing a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group bonded to a Si atom; at least one R Ｓｉ This is a monovalent group containing a Si atom to which a hydroxyl group or hydrolyzable group is bonded; X Ａ Each of these is independently a single bond or a divalent to decavalent organic group; α is an integer between 1 and 9; β is an integer between 1 and 9; Each of the γ values ​​is an independent integer between 1 and 9. The article according to any one of claims 1 to 5, comprising at least one silane compound represented by .

7. The silane compound is, in formula (1) or (2) above, R Ｓｉ However, the following formulas (S1), (S2), (S3), (S4), or (S5): 【Chemistry 2】 [In the formula: R １１ These are, independently, a hydroxyl group or a hydrolyzable group, R １２ Each of these is independently a monovalent organic group, n1 is (SiR １１ ｎ１ R １２ ３－ｎ１ Each unit is an independent integer between 0 and 3. X １１ Each of these is independently a single bond or a divalent organic group. R １３ Each of these is independently a hydrogen atom or a monovalent organic group. Each t is an independent integer greater than or equal to 2. R １４ Each of these is independently a hydrogen atom, a halogen atom, or -X １１ -SiR １１ ｎ１ R １２ ３－ｎ１ And, R １５ Each of these is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkylene oxy group having 1 to 6 carbon atoms. R ａ１ Each of them is independent of -Z １ -SiR ２１ ｐ１ R ２２ ｑ１ R ２３ ｒ１ And; Z １ These are, independently, divalent organic groups, R ２１ Each of them is independent of -Z １’ -SiR ２１’ ｐ１’ R ２２’ ｑ１’ R ２３’ ｒ１’ And; R ２２ These are, independently, a hydroxyl group or a hydrolyzable group, R ２３ Each of these is independently a monovalent organic group, p1 is an integer between 0 and 3, independently of each other. Each of q1 is an integer between 0 and 3, independently of the others. Each r1 is an independent integer between 0 and 3. Z １’ These are, independently, divalent organic groups, R ２１’ Each of them is independent of -Z １” -SiR ２２” ｑ１” R ２３” ｒ１” And; R ２２’ These are, independently, a hydroxyl group or a hydrolyzable group, R ２３’ Each of these is independently a monovalent organic group, p1' are each independent integers between 0 and 3. Each of q1' is an independent integer between 0 and 3. r1' are each independent integers between 0 and 3. Z １” These are, independently, divalent organic groups, R ２２” These are, independently, a hydroxyl group or a hydrolyzable group, R ２３” Each of these is independently a monovalent organic group, Each of q1'' is an independent integer between 0 and 3. Each of r1'' is an independent integer between 0 and 3. R ｂ１ These are, independently, a hydroxyl group or a hydrolyzable group, R ｃ１ Each of these is independently a monovalent organic group, k1 is an integer between 0 and 3, independently of each other. l1 are each an independent integer between 0 and 3. Each of the m1 values ​​is an integer between 0 and 3, independently of the others. However, in formula (S3), there are at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded, R ｄ１ Each of them is independent of -Z ２ -CR ３１ ｐ２ R ３２ ｑ２ R ３３ ｒ２ And, Z ２ Each of these is independently a single bond, an oxygen atom, or a divalent organic group. R ３１ Each of them is independent of -Z ２’ -CR ３２’ ｑ２’ R ３３’ ｒ２’ And, R ３２ each independently represents -Z ３ -SiR ３４ ｎ２ R ３５ ３－ｎ２ and R ３３ Each of these is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. p2 is an integer between 0 and 3, independently of each other. Each of the q2 values ​​is an integer between 0 and 3, independently of the others. Each of the r2 values ​​is an integer between 0 and 3, independently of the others. Z ２’ is, independently of one another, a single bond, an oxygen atom or a divalent organic group, R ３２’ Each of them is independent of -Z ３ -SiR ３４ ｎ２ R ３５ ３－ｎ２ And, R ３３’ Each of these is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Each of q2' is an integer between 0 and 3, independently of the others. r2' are each independent integers between 0 and 3. Z ３ Each of these is independently a single bond, an oxygen atom, or a divalent organic group; R ３４ These are, independently, a hydroxyl group or a hydrolyzable group, R ３５ Each of these is independently a monovalent organic group, n2 are each an independent integer between 0 and 3. R ｅ１ Each of them is independent of -Z ３ -SiR ３４ ｎ２ R ３５ ３－ｎ２ And, R ｆ１ Each of these is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. k2 are each an independent integer between 0 and 3. l2 are each an independent integer between 0 and 3. Each of the values ​​of m2 is an independent integer between 0 and 3. However, in formula (S4), there are at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded, R ｇ１ and R ｈ１ Each of them is independent of -Z ４ -SiR １１ ｎ１ R １２ ３－ｎ１ , -Z ４ -SiR ａ１ ｋ１ R ｂ１ ｌ１ R ｃ１ ｍ１ , or -Z ４ -CR ｄ１ ｋ２ R ｅ１ ｌ２ R ｆ１ ｍ２ And, Z ４ Each of these is independently a single bond, an oxygen atom, or a divalent organic group. However, in formula (S5), there are at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded. The article according to claim 6, comprising a compound which is a group represented by .

8. A method for manufacturing an article, The aforementioned article comprises a base material (A) and A water- and oil-repellent layer (C) formed from a silane compound containing Si atoms to which hydroxyl groups or hydrolyzable groups are bonded, Displaced between the substrate (A) and the water-repellent and oil-repellent layer (C), alkali metal atoms and Cl － NO ３ － and SO ３ A silicon oxide layer (B) comprising one or more selected from the group consisting of - In the silicon oxide layer (B), in a region with a depth of 0.1 to 0.3 nm from the surface in contact with the water-repellent and oil-repellent layer (C), the average concentration of alkali metal atoms is 1.4 × 10⁻¹⁶. １８ atoms / cm ３ The above 2.0 x 10 １９ atoms / cm ３ It is less than, The thickness of the silicon oxide layer (B) is 15 nm or less. The silicon oxide layer (B) is formed from a binder composition, The binder composition comprises a silicon dioxide precursor, an acid, and an alkali metal salt. The alkali metal salt comprises one or more selected from chloride salts, nitrates, and sulfates. The silane compound is a method for producing an article having a fluorine atom.

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