Article and method for manufacturing article

Abstract

The purpose of the present disclosure is to provide an article comprising a surface treatment layer having excellent durability.　An article comprises: a base material (A); a water-repellent oil-repellent layer (C); and a silicon oxide layer (B) disposed between the base material (A) and the water-repellent oil-repellent layer (C), the silicon oxide layer (B) containing alkali metal atoms and one or more selected from the group consisting of Cl−, NO3 −, SO3 −, SO4 2−, PO3 −, and PO4 3−. In the silicon oxide layer (B), the average value of the concentration of the alkali metal atoms in a region at a depth of 0.1-0.3 nm from the surface in contact with the water-repellent oil-repellent layer (C) is at least 1.4 × 1018 atoms / cm3 and less than 2.0 × 1019 atoms / cm3. The water-repellent oil-repellent layer (C) is formed by using a surface treatment agent that contains a silane compound having Si atoms to which hydroxyl groups or hydrolyzable groups are bonded. The silane compound has fluorine atoms.

Description

Article and method for manufacturing article

[0001] FIELD OF THE DISCLOSURE The present disclosure relates to articles and methods of making articles.

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

[0003] JP 2019-116097 A U.S. Patent Publication No. 2020 / 0333510

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

[0005] The present disclosure aims to provide an article having a surface treatment layer with good durability.

[0006] The present disclosure includes the following: [1] a substrate (A), a water- and oil-repellent layer (C), and a water- and oil-repellent layer (C) disposed between the substrate (A) and the water- and oil-repellent layer (C), the water- and oil-repellent layer (C) containing an alkali metal atom and Cl － , NO ３ － , S.O. ３ － , S.O. ４ ２－ , P.O. ３ － and P.O. ４ ３－ and a silicon oxide layer (B) containing one or more selected from the group consisting of: wherein the silicon oxide layer (B) has an average alkali metal atom concentration of 1.4 × 10 in a region having a depth of 0.1 to 0.3 nm from the surface in contact with the water- and oil-repellent layer (C). １８ atoms / cm ３ Above 2.0 x 10 １９ atoms / cm ３[2] The article according to [1], wherein 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, and the silane compound has a fluorine atom. [3] The article according to [1], wherein the alkali metal atom contains a sodium atom. [4] The article according to [1], wherein the silicon oxide layer (B) is formed using a surface treatment agent containing a silane compound having a fluorine atom. － , S.O. ３ － and NO ３ － [4] The article according to [1] or [2], comprising one or more selected from the group consisting of: － , S.O. ３ － and NO ３ － The article according to any one of [1] to [3], wherein the silicon oxide layer (B) comprises one or more selected from the group consisting of a condensate of a silicic acid compound and a hydrolyzate of an alkoxysilane. [5] The article according to any one of [1] to [4], wherein the silicon oxide layer (B) comprises one or more selected from the group consisting of a condensate of a silicic acid compound and a hydrolyzate of an alkoxysilane. [6] The article according to any one of [1] to [5], wherein the silicon oxide layer (B) is formed from a binder composition comprising a silicon oxide precursor, an acid, and an alkali metal salt. [7] The article according to any one of [1] to [6], wherein the silicon oxide layer (B) is formed from a liquid binder composition comprising a silicon oxide precursor, an acid, an alkali metal salt, and a solvent. [8] The article according to [6], wherein the silicon oxide precursor comprises one or more selected from the group consisting of a silicic acid compound, a condensate of a silicic acid compound, an alkoxysilane, and a hydrolyzed condensate of an alkoxysilane. [9] The silane compound in the water- and oil-repellent layer (C) is represented by the following formula (1) or (2): [In the formula: R Ｆ１ are each independently Rf １ -R Ｆ -O ｑ - and R Ｆ２ is -Rf ２ ｐ -R Ｆ -O ｑ -; Rf１ each independently represents a C optionally substituted by one or more fluorine atoms; １－１６ Rf is an alkyl group; ２ is a C optionally substituted by one or more fluorine atoms; １－６ is an alkylene group; R Ｆ are each independently a divalent fluoropolyether group; p is 0 or 1; q is each independently 0 or 1; R Ｓｉ are each independently a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent group containing a Si atom to which a monovalent organic group is bonded; and at least one R Ｓｉ is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded; X Ａ are each independently a single bond or a divalent to decavalent organic group; α is an integer of 1 to 9; β is an integer of 1 to 9; and γ is each independently an integer of 1 to 9.

[10] The silane compound is an organic compound represented by the formula (1) or (2), wherein R Ｓｉ is represented by the following formula (S1), (S2), (S3), (S4) or (S5): [In the formula: R １１ are each independently a hydroxyl group or a hydrolyzable group, R １２ are each independently a monovalent organic group, and n1 is (SiR １１ ｎ１ R １２ ３－ｎ１ ) units are each independently an integer of 0 to 3, １１ are each independently a single bond or a divalent organic group, １３ are each independently a hydrogen atom or a monovalent organic group, each t is independently an integer of 2 or more, R １４ are each independently a hydrogen atom, a halogen atom or -X １１ -SiR １１ ｎ１ R １２ ３－ｎ１ and R １５are each independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms; R ａ１ are each independently -Z １ -SiR ２１ ｐ１ R ２２ ｑ１ R ２３ ｒ１ and Z １ are each independently a divalent organic group, ２１ are each independently -Z １’ -SiR ２１’ ｐ１’ R ２２’ ｑ１’ R ２３’ ｒ１’ and R ２２ are each independently a hydroxyl group or a hydrolyzable group, R ２３ are each independently a monovalent organic group, p1 is each independently an integer of 0 to 3, q1 is each independently an integer of 0 to 3, r1 is each independently an integer of 0 to 3, Z １’ are each independently a divalent organic group, ２１’ are each independently -Z １” -SiR ２２” ｑ１” R ２３” ｒ１” and R ２２’ are each independently a hydroxyl group or a hydrolyzable group, R ２３’ are each independently a monovalent organic group, p1' are each independently an integer of 0 to 3, q1' are each independently an integer of 0 to 3, r1' are each independently an integer of 0 to 3, Z １” are each independently a divalent organic group, ２２” are each independently a hydroxyl group or a hydrolyzable group, R ２３” are each independently a monovalent organic group; q1" are each independently an integer of 0 to 3; r1" are each independently an integer of 0 to 3; R ｂ１are each independently a hydroxyl group or a hydrolyzable group, R ｃ１ are each independently a monovalent organic group, k1 is each independently an integer of 0 to 3, l1 is each independently an integer of 0 to 3, and m1 is each independently an integer of 0 to 3, provided that in formula (S3), there are at least two Si atoms bonded to a hydroxyl group or a hydrolyzable group, and R ｄ１ are each independently -Z ２ -CR ３１ ｐ２ R ３２ ｑ２ R ３３ ｒ２ and Z ２ are each independently a single bond, an oxygen atom, or a divalent organic group, and R ３１ are each independently -Z ２’ -CR ３２’ ｑ２’ R ３３’ ｒ２’ and R ３２ are each independently -Z ３ -SiR ３４ ｎ２ R ３５ ３－ｎ２ and R ３３ are each independently a hydrogen atom, a hydroxyl group, or a monovalent organic group; p2 is each independently an integer of 0 to 3; q2 is each independently an integer of 0 to 3; r2 is each independently an integer of 0 to 3; Z ２’ are each independently a single bond, an oxygen atom, or a divalent organic group, and R ３２’ are each independently -Z ３ -SiR ３４ ｎ２ R ３５ ３－ｎ２ and R ３３’ are each independently a hydrogen atom, a hydroxyl group, or a monovalent organic group; q2' are each independently an integer of 0 to 3; r2' are each independently an integer of 0 to 3; Z ３ are each independently a single bond, an oxygen atom, or a divalent organic group; R ３４are each independently a hydroxyl group or a hydrolyzable group, R ３５ are each independently a monovalent organic group, n2 is each independently an integer of 0 to 3, R ｅ１ are each independently -Z ３ -SiR ３４ ｎ２ R ３５ ３－ｎ２ and R ｆ１ are each independently a hydrogen atom, a hydroxyl group, or a monovalent organic group, k2 is each independently an integer of 0 to 3, l2 is each independently an integer of 0 to 3, and m2 is each independently an integer of 0 to 3. However, in formula (S4), there are at least two Si atoms bonded to a hydroxyl group or a hydrolyzable group, and R ｇ１ and R ｈ１ are each 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 R ｆ１ ｍ２ and Z ４ are each independently a single bond, an oxygen atom, or a divalent organic group, with the proviso that in formula (S5), there are at least two Si atoms bonded to a hydroxyl group or a hydrolyzable group.]

[11] A method for producing an article, the article comprising: a substrate (A); a water- and oil-repellent layer (C) formed from a silane compound containing a Si atom bonded to a hydroxyl group or a hydrolyzable group; and a water- and oil-repellent layer (C) disposed between the substrate (A) and the water- and oil-repellent layer (C), the water- and oil-repellent layer (C) containing an alkali metal atom and Cl. － , NO ３ － , S.O. ３ － , S.O.４ ２－ , P.O. ３ － and P.O. ４ ３－ and a silicon oxide layer (B) containing one or more selected from the group consisting of: wherein the silicon oxide layer (B) has an average alkali metal atom concentration of 1.4 × 10 in a region having a depth of 0.1 to 0.3 nm from the surface in contact with the water- and oil-repellent layer (C). １８ atoms / cm ３ Above 2.0 x 10 １９ atoms / cm ３ and the silane compound has a fluorine atom.

[0007] The present disclosure can provide an article with a surface treatment layer that has good durability.

[0008] The article of the present disclosure comprises: a substrate (A); a water- and oil-repellent layer (C); and a water- and oil-repellent layer (C) disposed between the substrate (A) and the water- and oil-repellent layer (C), the water- and oil-repellent layer (C) containing an alkali metal atom and Cl. － , NO ３ － , S.O. ３ － , S.O. ４ ２－ , P.O. ３ － and P.O. ４ ３－ and a silicon oxide layer (B) containing one or more selected from the group consisting of: wherein the silicon oxide layer (B) has an average alkali metal atom concentration of 1.4 × 10 in a region having a depth of 0.1 to 0.3 nm from the surface in contact with the water- and oil-repellent layer (C). １８ atoms / cm ３ Above 2.0 x 10 １９ atoms / cm ３ 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, and the silane compound has a fluorine atom.

[0009] The article of the present disclosure has good durability of the surface treatment layer. Although the present disclosure should not be interpreted as being limited to a particular theory, the reason why the article of the present disclosure can achieve such an effect is thought to be as follows. That is, when a silicon oxide layer is used in surface treatment with a silane compound having fluorine atoms, adhesion between the surface treatment layer and the substrate can be improved. It has also been found that the durability of the surface treatment layer can be improved by including alkali metal atoms in the silicon oxide layer. It is believed that the inclusion of alkali metal atoms in the silicon oxide layer increases the number of silanol groups on the surface of the silicon oxide layer, increasing the number of reaction sites, thereby improving adhesion between the silicon oxide layer and the water- and oil-repellent layer and improving durability.

[0010] Substrate (A) The substrate (A) that can be used in the present disclosure is not particularly limited. The substrate (A) may be, for example, glass, resin (natural or synthetic resin, for example, a general plastic material, preferably polycarbonate resin, poly(meth)acrylate resin, polyethylene terephthalate resin, triacetyl cellulose resin, polyimide resin, modified (transparent) polyimide resin, polycycloolefin resin, polyethylene naphthalate resin, and may be in the form of a plate, film, or other form), metal (a simple metal such as aluminum, copper, silver, iron, or the like, or a composite such as an alloy), ceramics, semiconductors (silicon, germanium, etc.), fibers (woven fabrics, nonwoven fabrics, etc.), fur, leather, wood, ceramics, stone, building materials, etc., and may be made of any suitable material.

[0011] For example, when the article to be manufactured is an optical component, the material constituting the surface of the (A) substrate may be a material for optical components, 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-reflection layer, a polarizing film, a retardation film, an organic EL display module, a liquid crystal display module, or the like, depending on its specific specifications. The anti-reflection layer may be either a single-layer anti-reflection layer or a multi-layer anti-reflection layer. Examples of inorganic materials that can be used for the anti-reflection layer include SiO ２ , SiO, ZrO ２ , TiO ２ , TiO, Ti２ O ３ , Ti ２ O ５ , Al ２ O ３ , Ta ２ O ５ , Ta ３ O ５ , Nb ２ O ５ , HfO ２ , Si ３ N ４ , CeO ２ , MgO, Y ２ O ３ , SnO ２ , MgF ２ , W.O. ３ These inorganic substances may be used alone or in combination of two or more (for example, as a mixture). In the case of a multi-layer antireflection layer, the outermost layer may contain SiO ２ and / or SiO is preferably used. When the article to be manufactured is an optical glass component for a touch panel, a transparent electrode, for example, a thin film using indium tin oxide (ITO) or indium zinc oxide, may be provided on a portion of the surface of the substrate (glass). Furthermore, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomization film layer, a hard coating film layer, a polarizing film, a phase difference film, a liquid crystal display module, or the like, depending on its specific specifications.

[0012] The shape of the substrate (A) is not particularly limited. The surface region of the substrate on which the film (surface treatment layer) is to be formed may be at least a part of the surface of the substrate (A), and may be appropriately determined depending on the use and specific specifications of the article to be manufactured.

[0013] In one embodiment, at least the surface portion of such a substrate may be made of a material that originally contains hydroxyl groups. Examples of such materials include glass, metals (especially base metals), ceramics, semiconductors, and the like, on whose surfaces native oxide or thermal oxide films form. Alternatively, in cases where the presence of hydroxyl groups is insufficient, such as in resins, or in cases where hydroxyl groups are not originally present, some kind of pretreatment can be performed on the substrate to introduce or increase the number of hydroxyl groups on the substrate surface. Examples of such pretreatments include plasma treatment (e.g., corona discharge) and ion beam irradiation. Plasma treatment can introduce or increase hydroxyl groups on the substrate surface, and can also be 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 preliminarily formed in the form of a monomolecular film on the substrate surface by the Langmuir-Blodgett method (LB method) or chemical adsorption method, and then the unsaturated bonds are cleaved in an atmosphere containing oxygen, nitrogen, or the like.

[0014] In another embodiment, at least the surface portion of such a substrate may be made of a material containing 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, such as sapphire glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, quartz glass, or 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 disposed between the substrate (A) and the water- and oil-repellent layer (C), and is a layer mainly composed of silicon oxide. － , S.O. ３ － , NO ３ － , S.O. ４ ２－ , P.O.３ － and P.O. ４ ３－ and one or more selected from the group consisting of:

[0017] The alkali metal atom includes lithium, sodium, potassium, etc., and preferably contains sodium.

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

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

[0020] The average concentration of alkali metal atoms in the region 0.1 to 0.3 nm deep from the surface in contact with the 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 at a depth of 0.1 to 0.3 nm from the surface in contact with the water-repellent and oil-repellent layer (C). － , S.O.３ － , NO ３ － , S.O. ４ ２－ , P.O. ３ － and P.O. ４ ３－ Preferably, the compound contains one or more selected from the group consisting of Cl － , S.O. ３ － and NO ３ － It is more preferable that the composition contains one or more selected from the group consisting of NO ３ － It is more preferred that the composition comprises:

[0022] The above Cl － , S.O. ３ － , NO ３ － , S.O. ４ ２－ , P.O. ３ － and P.O. ４ ３－ The content of one or more selected from the group consisting of may be preferably 1.0% or more and 20.0% or less, more preferably 1.0% or more and 10.0% or less, and even more preferably 1.0% or more and 5.0% or less, relative to the total count number.

[0023] The above Cl － , S.O. ３ － , NO ３ － , S.O. ４ ２－ , P.O. ３ － and P.O. ４ ３－ The content of one or more selected from the group consisting of can be measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS).

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

[0025] Examples of the silicon oxide precursor include silicic acid, partial condensates of silicic acid, alkali metal silicates, silane compounds having a hydrolyzable group bonded to a silicon atom, and partial hydrolysis condensates of the silane compounds. Silicic acid and its partial condensates can be converted into silicon oxide by dehydration condensation. Alkali metal silicates can be converted into silicic acid or its partial condensates by the addition of an acid or a cation exchange resin, and the resulting silicic acid or its partial condensates can then be dehydration condensed into silicon oxide. Examples of the hydrolyzable group in a silane compound having a hydrolyzable group bonded to a silicon atom include an alkoxy group and a chlorine atom. The hydrolyzable group in the silane compound can be hydrolyzed to a hydroxyl group, and the resulting silanol compound can be dehydration condensed to form silicon oxide. Examples of silane compounds having a hydrolyzable group bonded to a silicon atom include alkoxysilanes such as tetraalkoxysilanes and alkyltrialkoxysilanes, and tetrachlorosilane.

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

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

[0028] The content of the acid is preferably 0.01 to 10.0 mol, more preferably 0.02 to 5.0 mol, and even more preferably 0.05 to 1.0 mol, per mol of silicon atoms contained in the silicon oxide precursor. When the content of the acid is within this range, it can be easy to control the concentration of alkali metal atoms in the silicon oxide layer (B).

[0029] The alkali metal salt may be any salt containing an alkali metal ion. Examples of the alkali metal ion contained in the alkali metal salt include lithium ion, sodium ion, and potassium ion, with sodium ion being preferred. Examples of the alkali metal ion include chloride salts, sulfite salts, nitrate salts, sulfate salts, and phosphate salts containing these alkali metal ions, with chloride salts and nitrate salts being preferred. Examples of the alkali metal salt include sodium chloride and sodium nitrate.

[0030] The content of the alkali metal salt is preferably 0.01 to 2.0 mol, more preferably 0.05 to 1.0 mol, and even more preferably 0.1 to 0.5 mol, per mol of silicon atoms contained in the silicon oxide precursor. When the content of the alkali metal salt is within this range, it can be easy to control the concentration of alkali metal atoms in the silicon oxide layer (B).

[0031] The conjugate base of the acid and Cl contained in the alkali metal salt － , S.O. ３ － , NO ３ － , S.O. ４ ２－ , P.O. ３ － and P.O. ４ ３－ In one embodiment, the conjugate base of the acid and the Cl contained in the alkali metal salt are the same or different. － , S.O. ３ － , NO ３ － , S.O. ４ ２－ , P.O. ３ － and P.O. ４ ３－ In another embodiment, the conjugate base of the acid and the Cl contained in the alkali metal salt are the same. － , S.O. ３ － , NO３ － , S.O. ４ ２－ , P.O. ３ － and P.O. ４ ３－ is different from one or more selected from the group consisting of:

[0032] In the binder composition, the total content of the silicon oxide precursor, acid, and alkali metal salt may be preferably 1 mass % or more and 60 mass % or less, more preferably 5 mass % or more and 50 mass % or less, and even more preferably 10 mass % or more and 40 mass % or less, of 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 solvent 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; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; etc. 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 more preferred.

[0035] In the liquid binder composition, the solvent content may be preferably 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 oxide layer (B) can be formed by applying the binder composition to the surface of the substrate (A) so as to coat it. The coating method is not particularly limited. For example, a wet coating method or a dry coating method can be used.

[0037] Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, wipe coating, squeegee coating, die coating, ink jet, casting, Langmuir-Blodgett coating, 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 beam, high frequency heating using microwaves, etc., ion beam, and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.

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

[0040] In one embodiment, when using the wet coating method, the solvent is, for example, R ９０ A compound represented by —OH can be used. ９０ is a monovalent organic group, preferably C １－２０ Alkyl group or C ３－２０ The alkylene group may be substituted with one or more substituents. Examples of the substituents include a hydroxyl group, -OR ９１ (where R ９１ is C １－１０ Alkyl group, preferably C １－３ alkyl groups, such as methyl groups.

[0041] When the dry coating method is used, the binder composition may be subjected to the dry coating method as it is, or may be subjected to the dry coating method after being diluted with the above-mentioned solvent.

[0042] The silicon oxide layer (B) is preferably formed so that the silicon oxide precursor is present in the layer together with an acid as a catalyst for hydrolysis and dehydration condensation. Conveniently, in the case of a wet coating method, the binder composition may be diluted with a solvent, and then a catalyst may be added to the diluted binder composition immediately before application to the substrate surface. In the case of a dry coating method, the binder composition containing the catalyst may be directly vapor-deposited (usually vacuum vapor-deposited), or a pellet-shaped material containing the catalyst-added surface treatment agent impregnated on a porous metal such as iron or copper may be vapor-deposited (usually vacuum vapor-deposited).

[0043] The binder composition may contain a catalyst other than an acid. Examples of such a catalyst include any suitable base, transition metal (e.g., Ti, Ni, Sn, Zr, Al, B, etc.), sulfur-containing compounds having an unshared electron pair in their molecular structure, or nitrogen-containing compounds (e.g., sulfoxide compounds, aliphatic amine compounds, aromatic amine compounds, phosphoric acid amide compounds, amide compounds, and urea compounds). Examples of the base catalyst include ammonia, sodium hydroxide, potassium hydroxide, and organic amines such as triethylamine and diethylamine. Examples of the transition metal, aliphatic amine compound, and aromatic amine compound 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 water- and oil-repellent layer (C) is disposed on the 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 silane compound contains a fluorine atom. Such a silane compound may typically have a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded. The hydrolysis condensate of the silane compound can be formed by hydrolysis and / or condensation of the hydroxyl group or the hydrolyzable group to form a siloxane bond (-Si-O-Si-).

[0046] The silane compound may be a silane compound having a fluorine atom, and preferably a fluoropolyether group-containing silane compound.

[0047] Preferably, the silane compound is represented by the following formula (1) or (2): [In the formula: R Ｆ１ are each independently Rf １ -R Ｆ -O ｑ - and R Ｆ２ is -Rf ２ ｐ -R Ｆ -O ｑ -; Rf １ each independently represents a C optionally substituted by one or more fluorine atoms; １－１６ Rf is an alkyl group; ２ is a C optionally substituted by one or more fluorine atoms; １－６ is an alkylene group; R Ｆ are each independently a divalent fluoropolyether group; p is 0 or 1; q is each independently 0 or 1; R Ｓｉ are each independently a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent group containing a Si atom to which a monovalent organic group is bonded; and at least one R Ｓｉ is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded; X Ａ are each independently a single bond or a divalent to decavalent organic group; α is an integer of 1 to 9; β is an integer of 1 to 9; and γ is each independently an integer of 1 to 9.

[0048] In the above formula (1), R Ｆ１ are each independently Rf １ -R Ｆ -O ｑ - is.

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

[0050] In the above formula, Rf １ each independently represents a C optionally substituted by one or more fluorine atoms; １－１６ It is an alkyl group.

[0051] The C optionally substituted with one or more fluorine atoms １－１６ "C" in the alkyl group １－１６ The "alkyl group" may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C １－６ Alkyl groups, especially C １－３ alkyl group, more preferably a straight-chain C １－６ Alkyl groups, especially C １－３ It is an alkyl group.

[0052] The above Rf １ is preferably a C substituted by one or more fluorine atoms １－１６ alkyl group, more preferably CF ２ H-C １－１５ A perfluoroalkylene group, more preferably C １－１６ It is a perfluoroalkyl group.

[0053] Above C １－１６ The perfluoroalkyl group may be a straight chain or a branched chain, and preferably is a straight chain or branched chain C １－６ Perfluoroalkyl groups, especially C １－３ perfluoroalkyl groups, more preferably linear C １－６ Perfluoroalkyl groups, especially C １－３ Perfluoroalkyl groups, specifically —CF ３ , -CF ２ CF ３ , or -CF ２ CF ２ CF ３ is.

[0054] In the above formula, Rf ２ is a C optionally substituted by one or more fluorine atoms; １－６ It is an alkylene group.

[0055] The C optionally substituted with one or more fluorine atoms １－６ "C" in the alkylene group １－６ The "alkylene group" may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C １－３ alkylene groups, more preferably linear C １－３ It is an alkylene group.

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

[0057] Above C １－６ The perfluoroalkylene group may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C １－３ A perfluoroalkylene group, more preferably a linear C １－３ Perfluoroalkylene groups, specifically —CF ２ -, -CF ２ CF ２ - or -CF ２ CF ２ CF ２ - is.

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

[0059] In the above formula, each q is independently 0 or 1. In one embodiment, q is 0. In another embodiment, q is 1.

[0060] In the above formulas (1) and (2), R Ｆ are each independently a divalent fluoropolyether group.

[0061] R Ｆ is preferably represented by the formula: -(OC ６ F １２ ) ａ - (OC ５ F １０ )ｂ - (OC ４ F ８ ) ｃ - (OC ３ R Ｆａ ６ ) ｄ - (OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - [In the formula: R Ｆａ are each independently a hydrogen atom, a fluorine atom, or a chlorine atom, a, b, c, d, e, and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e, and f is 1 or more. The order of occurrence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula. However, all R Ｆａ is a hydrogen atom or a chlorine atom, then at least one of a, b, c, e and f is 1 or greater.]

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

[0063] a, b, c, d, e and f may preferably each independently be an integer of 0 to 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 or branched, and may contain a ring structure. For example, -(OC ６ F １２ )- is -(OCF ２ CF ２ CF ２ CF ２ CF２ CF ２ )-(OCF(CF ３ )(CF ２ CF ２ CF ２ CF ２ )-(OCF ２ CF(CF ３ )(CF ２ CF ２ CF ２ )-(OCF ２ CF ２ CF(CF ３ )(CF ２ CF ２ )-(OCF ２ CF ２ CF ２ CF(CF ３ )(CF ２ )-(OCF ２ CF ２ CF ２ CF ２ CF(CF ３ ))-(OC ５ F １０ )-(OCF ２ CF ２ CF ２ CF ２ CF ２ )-(OCF(CF ３ )(CF ２ CF ２ CF ２ )-(OCF ２ CF(CF ３ )(CF ２ CF ２ )-(OCF ２ CF ２ CF(CF ３ )(CF ２ )-(OCF ２ CF ２ CF ２ CF(CF ３ ))-(OC ４ F ８ )-(OCF ２ CF ２ CF ２ CF ２ )-(OCF(CF ３ )(CF２ CF ２ ) -, -(OCF ２ CF (CF ３ )CF ２ ) -, -(OCF ２ CF ２ CF (CF ３ )) -, -(OC(CF ３ ) ２ CF ２ ) -, -(OCF ２ C (CF ３ ) ２ )-,-(OCF(CF ３ )CF(CF ３ ))-,-(OCF(C ２ F ５ )CF ２ )-and-(OCF ２ CF (C ２ F ５ ))-. ３ F ６ ) - (i.e., in the above formula, R Ｆａ is a fluorine atom) is -(OCF ２ CF ２ CF ２ )-,-(OCF(CF ３ )CF ２ )-and-(OCF ２ CF (CF ３ ))-. ２ F ４ )- is -(OCF ２ CF ２ )-and-(OCF(CF ３ ))-.

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

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

[0068] The ring structure may be preferably 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 unit having a ring structure may preferably be the following unit.

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

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

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

[0073] In one embodiment, R Ｆ are each independently a group represented by any one of the following formulas (f1) to (f5): —(OC ３ F ６ ) ｄ - (OC ２ F ４ ) ｅ - (f1) [wherein d is an integer of 1 to 200, and e is 0 or 1]; - (OC ４ F ８ ) ｃ - (OC ３ F ６ ) ｄ - (OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - (f2) [wherein c and d each independently represent an integer of 0 or more and 30 or less, e and f each independently represent an integer of 1 or more and 200 or less, the sum of c, d, e and f is 2 or more, and the order of occurrence of each repeating unit enclosed in parentheses with the subscript c, d, e or f is arbitrary in the formula.]; - (R ６ -R ７ ) ｇ - (f3) [wherein, R ６ is OCF ２ or O.C. ２ F ４ and R ７ is O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８, O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups independently selected from these groups, and g is an integer of 2 to 100. ６ -R ７ ) ｇ -R ｒ - (R ７’ -R ６’ ) ｇ’ - (f4) [wherein, R ６ is OCF ２ or O.C. ２ F ４ and R ７ is O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups independently selected from these groups; ６’ is OCF ２ or O.C. ２ F ４ and R ７’ is O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups independently selected from these groups, g is an integer from 2 to 100, g' is an integer from 2 to 100, R ｒ teeth,

[0074] (wherein * indicates the bond position). ]; -(OC ６ F １２ ) ａ - (OC５ F １０ ) ｂ - (OC ４ F ８ ) ｃ - (OC ３ F ６ ) ｄ - (OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - (f5) [In the formula, e is an integer of 1 or more and 200 or less, a, b, c, d, and f are each independently an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] - (OC ６ F １２ ) ａ - (OC ５ F １０ ) ｂ - (OC ４ F ８ ) ｃ - (OC ３ F ６ ) ｄ - (OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - (f6) (In the formula, f is an integer of 1 or more and 200 or less, a, b, c, d, and e each independently are an integer of 0 or more and 200 or less, and the order 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 of 5 to 200, more preferably 10 to 100, and even more preferably 15 to 50, for example, an integer of 25 to 35. ３ F ６ is preferably (OCF ２ CF ２ CF ２ ), (OCF (CF ３ )CF ２ ) or (OCF ２ CF (CF ３ )), more preferably (OCF２ CF ２ CF ２ ) in the above formula (f1). ２ F ４ ) is preferably (OCF ２ CF ２ ) or (OCF(CF ３ )), more preferably (OCF ２ CF ２ In one embodiment, e is 0. In another embodiment, e is 1.

[0076] In the formula (f2), e and f are each independently an integer of preferably 5 to 200, more preferably 10 to 200. The sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. In one aspect, the formula (f2) is preferably -(OCF ２ CF ２ CF ２ CF ２ ) ｃ -(OCF ２ CF ２ CF ２ ) ｄ -(OCF ２ CF ２ ) ｅ -(OCF ２ ) ｆ In another embodiment, formula (f2) is a group represented by -(OC ２ F ４ ) ｅ -(OCF ２ ) ｆ It may be a group represented by -.

[0077] In the above formula (f3), R ６ is preferably OC ２ F ４ In the above (f3), R ７ is preferably OC ２ F ４ , O.C. ３ F ６ and O.C. ４ F ８or a combination of two or three groups independently selected from these groups, more preferably OC ３ F ６ and O.C. ４ F ８ is a group selected from ２ F ４ , O.C. ３ F ６ and O.C. ４ F ８ The combination of two or three groups independently selected from the group consisting of, but not limited to, —OC ２ F ４ O.C. ３ F ６ -, -OC ２ F ４ O.C. ４ F ８ -, -OC ３ F ６ O.C. ２ F ４ -, -OC ３ F ６ O.C. ３ F ６ -, -OC ３ F ６ O.C. ４ F ８ -, -OC ４ F ８ O.C. ４ F ８ -, -OC ４ F ８ O.C. ３ F ６ -, -OC ４ F ８ O.C. ２ F ４ -, -OC ２ F ４ O.C. ２ F ４ O.C. ３ F ６ -, -OC ２ F ４ O.C. ２ F ４ O.C. ４ F ８ -, -OC ２ F ４ O.C. ３ F ６ O.C.２ F ４ -, -OC ２ F ４ O.C. ３ F ６ O.C. ３ F ６ -, -OC ２ F ４ O.C. ４ F ８ O.C. ２ F ４ -, -OC ３ F ６ O.C. ２ F ４ O.C. ２ F ４ -, -OC ３ F ６ O.C. ２ F ４ O.C. ３ F ６ -, -OC ３ F ６ O.C. ３ F ６ O.C. ２ F ４ - and -OC ４ F ８ O.C. ２ F ４ O.C. ２ F ４ In the formula (f3), g is preferably an integer of 3 or more, more preferably an integer of 5 or more. The g is preferably an integer of 50 or less. In the formula (f3), OC ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ may be either a straight chain or a branched chain, and is preferably a straight chain. In this embodiment, the above formula (f3) is preferably -(OC ２ F ４ -OC ３ F ６ ) ｇ -or- (OC ２ F ４ -OC ４ F ８ )ｇ - is.

[0078] In the above formula (f4), R ６ , R ７ and g have the same meanings as those in formula (f3) above, and have the same embodiments. ６’ , R ７’ and g′ are R ６ , R ７ and g have the same meaning and similar aspects. ｒ is preferably

[0079] [wherein * indicates the bonding position], and more preferably

[0080] [wherein * indicates the bonding position.]

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

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

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

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

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

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

[0087] In one embodiment, the R Ｆis a group represented by the above formula (f5).

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

[0089] The above R Ｆ In the formula, 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, abrasion 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 more improved the slipperiness and abrasion 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 increased. The larger the e / f ratio, the more improved the stability of the compound.

[0090] In the above silane compound, R Ｆ１ and R Ｆ２ The number average molecular weight of the portion is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. Ｆ１ and R Ｆ２ The number average molecular weight of １９ The value is measured by F-NMR.

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

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

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

[0094] Here, the term "hydrolyzable group" refers to a group that can undergo a hydrolysis reaction, that is, a group that can be eliminated from the main skeleton of a compound by a hydrolysis reaction. Examples of the hydrolyzable group include -OR ｊ , -OCOR ｊ , —O—N═CR ｊ ２ , -NR ｊ ２ , -NHR ｊ , —NCO, halogen (wherein R ｊ is a substituted or unsubstituted C １－４ (representing an alkyl group) and the like.

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

[0096] In a preferred embodiment, R Ｓｉ is represented by the following formula (S1), (S2), (S3), or (S4): It is a group represented by the formula:

[0097] In the above formula, R １１ are each independently a hydroxyl group or a hydrolyzable group.

[0098] R １１ are preferably each independently a hydrolyzable group.

[0099] R １１ are preferably each independently -OR ｊ , -OCOR ｊ , —O—N═CR ｊ ２ , -NR ｊ ２ , -NHR ｊ , —NCO, or halogen (wherein R ｊ is a substituted or unsubstituted C１－４ alkyl group), and more preferably -OR ｊ (i.e., an alkoxy group). ｊ Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R ｊ is a methyl group, and in another embodiment, R ｊ is an ethyl group.

[0100] In the above formula, R １２ are each independently a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

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

[0102] In the above formula, n1 is (SiR １１ ｎ１ R １２ ３－ｎ１ ) units are each independently an integer of 0 to 3, provided that R Ｓｉ is a group represented by formula (S1) or (S2), the terminal R Ｓｉ In the moiety (hereinafter also simply referred to as the "terminal moiety" of formula (1) and formula (2)), n1 is 1 to 3 (SiR １１ ｎ１ R １２ ３－ｎ１ ) unit is present. That is, in such a terminal portion, all n1s do not simultaneously become 0. In other words, in the terminal portion of formula (1) and formula (2), there is at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

[0103] n1 is (SiR １１ ｎ１ R １２ ３－ｎ１) units are each independently an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0104] In the above formula, X １１ are each independently a single bond or a divalent organic group. Such a divalent organic group is preferably -R ２８ -O ｘ -R ２９ - (wherein, R ２８ and R ２９ are each independently a single bond or C １－２０ is an alkylene group, and x is 0 or 1. １－２０ The alkylene group may be a straight chain or a branched chain, but is preferably a straight chain. 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 are each independently -C １－６ Alkylene -O-C １－６ Alkylene- or -O-C １－６ It is alkylene-.

[0106] In a preferred embodiment, X １１ are each independently a single bond or a linear C １－６ an alkylene group, preferably a single bond or a straight-chain C １－３ Alkylene group, more preferably a single bond or a straight chain C １－２ It is preferably a linear C alkylene group. １－２ It is an alkylene group.

[0107] In the above formula, R １３ are each 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 straight-chain or branched, but is preferably straight-chain.

[0108] In a preferred embodiment, R １３are each independently a hydrogen atom or a straight-chain C １－６ is an alkyl group, preferably a hydrogen atom or a straight-chain C １－３ It is an alkyl group, preferably a hydrogen atom or a methyl group.

[0109] In the above formula, each t is independently an integer of 2 or more.

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

[0111] In the above formula, R １４ are each independently a hydrogen atom, a halogen atom or -X １１ -SiR １１ ｎ１ R １２ ３－ｎ１ Such a halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom. In a preferred embodiment, R １４ is a hydrogen atom.

[0112] In the above formula, R １５ are each independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms.

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

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

[0115] In one embodiment, formula (S1) is the following formula (S1-a): [In the formula, R １１ , R １２ , R １３ , X １１and n1 are as defined in formula (S1) above; t1 and t2 are each independently an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 2 to 10, for example, an integer of 1 to 5 or an integer of 2 to 5; the order of the repeating units enclosed in parentheses with t1 and t2 is arbitrary in the formula.]

[0116] In a preferred embodiment, formula (S1) is the following formula (S1-b): [In the formula, R １１ , R １２ , R １３ , X １１ , n1 and t are defined as in formula (S1) above.

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

[0118] Above Z １ are each independently an oxygen atom or a divalent organic group. １ The structure written as ２１ ｐ１ R ２２ ｑ１ R ２３ ｒ１ )

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

[0120] In a preferred embodiment, Z １ Is Z １ Preferably, in formula (S3), (Si-Z １ —Si) does not contain a siloxane bond.

[0121] Above Z １ is preferably C １－６ Alkylene group, -(CH ２ ) ｚ１ -O-(CH２ ) ｚ２ - (wherein z1 is an integer of 0 to 6, for example, an integer of 1 to 6, and z2 is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH ２ ) ｚ３ -phenylene-(CH ２ ) ｚ４ - (wherein z3 is an integer of 0 to 6, for example, an integer of 1 to 6, and z4 is an integer of 0 to 6, for example, an integer of 1 to 6). １－６ The alkylene group may be straight-chain or branched, but is preferably straight-chain. These groups may contain, for example, fluorine atoms, C １－６ Alkyl group, C ２－６ Alkenyl groups, and C ２－６ It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0122] In a preferred embodiment, Z １ is C １－６ Alkylene group or -(CH ２ ) ｚ３ -phenylene-(CH ２ ) ｚ４ -, preferably -phenylene-(CH ２ ) ｚ４ - is. Z １ is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.

[0123] In another preferred embodiment, the Z １ is C １－３ In one embodiment, Z is an alkylene group. １ is -CH ２ CH ２ CH ２ In another embodiment, Z １ is -CH ２ CH ２ -It can be.

[0124] The above R ２１ are each independently -Z １’ -SiR ２１’ ｐ１’ R ２２’ ｑ１’ R ２３’ｒ１’ is.

[0125] Above Z １’ are each independently an oxygen atom or a divalent organic group. １’ The structure written as ２１’ ｐ１’ R ２２’ ｑ１’ R ２３’ ｒ１’ )

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

[0127] In a preferred embodiment, Z １’ Is Z １’ Preferably, in formula (S3), (Si-Z １’ —Si) does not contain a siloxane bond.

[0128] Above Z １’ is preferably C １－６ Alkylene group, -(CH ２ ) ｚ１’ -O-(CH ２ ) ｚ２’ - (wherein z1' is an integer of 0 to 6, for example, an integer of 1 to 6, and z2' is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH ２ ) ｚ３’ -phenylene-(CH ２ ) ｚ４’ - (wherein z3' is an integer of 0 to 6, for example, an integer of 1 to 6, and z4' is an integer of 0 to 6, for example, an integer of 1 to 6). １－６ The alkylene group may be straight-chain or branched, but is preferably straight-chain. These groups may contain, for example, fluorine atoms, C １－６ Alkyl group, C ２－６ Alkenyl groups, and C ２－６ It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0129] In a preferred embodiment, Z １’ is C １－６Alkylene group or -(CH ２ ) ｚ３’ -phenylene-(CH ２ ) ｚ４’ -, preferably -phenylene-(CH ２ ) ｚ４’ - is. Z １’ is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.

[0130] In another preferred embodiment, the Z １’ is C １－３ In one embodiment, Z is an alkylene group. １’ is -CH ２ CH ２ CH ２ In another embodiment, Z １’ is -CH ２ CH ２ -It can be.

[0131] The above R ２１’ are each independently -Z １” -SiR ２２” ｑ１” R ２３” ｒ１” is.

[0132] Above Z １” are each independently an oxygen atom or a divalent organic group. １” The structure written as ２２” ｑ１” R ２３” ｒ１” )

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

[0134] In a preferred embodiment, Z １” Is Z １” Preferably, in formula (S3), (Si-Z １” —Si) does not contain a siloxane bond.

[0135] Above Z １” is preferably C １－６ Alkylene group, -(CH ２) ｚ１” -O-(CH ２ ) ｚ２” - (wherein z1" is an integer of 0 to 6, for example, an integer of 1 to 6, and z2" is an integer of 0 to 6, for example, an integer of 1 to 6), or - (CH ２ ) ｚ３” -phenylene-(CH ２ ) ｚ４” - (wherein z3" is an integer of 0 to 6, for example, an integer of 1 to 6, and z4" is an integer of 0 to 6, for example, an integer of 1 to 6). １－６ The alkylene group may be straight-chain or branched, but is preferably straight-chain. These groups may contain, for example, fluorine atoms, C １－６ Alkyl group, C ２－６ Alkenyl groups, and C ２－６ It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0136] In a preferred embodiment, Z １” is C １－６ Alkylene group or -(CH ２ ) ｚ３” -phenylene-(CH ２ ) ｚ４” -, preferably -phenylene-(CH ２ ) ｚ４” - is. Z １” is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.

[0137] In another preferred embodiment, the Z １” is C １－３ In one embodiment, Z is an alkylene group. １” is -CH ２ CH ２ CH ２ In another embodiment, Z １” is -CH ２ CH ２ -It can be.

[0138] The above R ２２” are each independently a hydroxyl group or a hydrolyzable group.

[0139] The above R ２２”are preferably each independently a hydrolyzable group.

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

[0141] The above R ２３” are each independently a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

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

[0143] Each of the q1"s is independently an integer of 0 to 3, and each of the r1"s is independently an integer of 0 to 3. The sum of q1" and r1" is (SiR ２２” ｑ１” R ２３” ｒ１” ) units, it is 3.

[0144] The above q1″ is (SiR ２２” ｑ１” R ２３”ｒ１” ) units are each independently an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0145] The above R ２２’ are each independently a hydroxyl group or a hydrolyzable group.

[0146] R ２２’ are preferably each independently a hydrolyzable group.

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

[0148] The above R ２３’ are each independently a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0149] R ２３’ In the formula (I), the monovalent organic group is preferably C １－２０ alkyl group, more preferably C １－６ It is preferably an alkyl group, more preferably a methyl group.

[0150] Each of the p1's is independently an integer of 0 to 3, each of the q1's is independently an integer of 0 to 3, and each of the r1's is independently an integer of 0 to 3. The sum of p', q1', and r1' is (SiR ２１’ ｐ１’ R ２２’ ｑ１’ R ２３’ ｒ１’ ) units, 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’ ) units may each 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’ ) units are each independently an integer of 1 to 3, preferably an integer of 2 or 3, and more preferably 3.

[0154] In one embodiment, p1′ is 0 and q1′ is (SiR ２１’ ｐ１’ R ２２’ ｑ１’ R ２３’ ｒ１’ ) units are each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.

[0155] The above R ２２ are each independently a hydroxyl group or a hydrolyzable group.

[0156] R ２２ are preferably each independently a hydrolyzable group.

[0157] R ２２ are preferably each independently -OR ｊ , -OCORｊ , —O—N═CR ｊ ２ , -NR ｊ ２ , -NHR ｊ , —NCO, or halogen (wherein R ｊ is a substituted or unsubstituted C １－４ alkyl group), and more preferably -OR ｊ (i.e., an alkoxy group). ｊ Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R ｊ is a methyl group, and in another embodiment, R ｊ is an ethyl group.

[0158] The above R ２３ are each independently a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

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

[0160] Each of the above p1's is independently an integer of 0 to 3, each of the q1's is independently an integer of 0 to 3, and each of the r1's is independently an integer of 0 to 3. The sum of p1, q1, and r1 is (SiR ２１ ｐ１ R ２２ ｑ１ R ２３ ｒ１ ) units, it is 3.

[0161] In one embodiment, p1 is 0.

[0162] In one embodiment, p1 is (SiR ２１ ｐ１ R ２２ ｑ１ R２３ ｒ１ ) units may each 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 embodiment, q1 is (SiR ２１ ｐ１ R ２２ ｑ１ R ２３ ｒ１ ) units are each independently an integer of 1 to 3, preferably an integer of 2 or 3, and more preferably 3.

[0164] In one embodiment, p1 is 0 and q1 is (SiR ２１ ｐ１ R ２２ ｑ１ R ２３ ｒ１ ) units are each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.

[0165] In the above formula, R ｂ１ are each independently a hydroxyl group or a hydrolyzable group.

[0166] The above R ｂ１ are preferably each independently a hydrolyzable group.

[0167] The above R ｂ１ are preferably each independently -OR ｊ , -OCOR ｊ , —O—N═CR ｊ ２ , -NR ｊ ２ , -NHR ｊ , —NCO, or halogen (wherein R ｊ is a substituted or unsubstituted C １－４ alkyl group), and more preferably -OR ｊ (i.e., an alkoxy group). ｊExamples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R ｊ is a methyl group, and in another embodiment, R ｊ is an ethyl group.

[0168] In the above formula, R ｃ１ are each independently a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

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

[0170] Each k1 is independently an integer of 0 to 3, each l1 is independently an integer of 0 to 3, and each m1 is independently an integer of 0 to 3. The sum of k1, l1, and m1 is (SiR ａ１ ｋ１ R ｂ１ ｌ１ R ｃ１ ｍ１ ) units, it is 3.

[0171] In one embodiment, k1 is (SiR ａ１ ｋ１ R ｂ１ ｌ１ R ｃ１ ｍ１ ) units are each independently an integer of 1 to 3, preferably 2 or 3, more preferably 3. In a preferred embodiment, k1 is 3.

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

[0173] In a preferred embodiment, the group represented by formula (S3) is -Z １ -SiR ２２ ｑ１ R ２３ ｒ１ (wherein q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1 is an integer of 0 to 2), -Z １’ -SiR ２２’ ｑ１’ R ２３’ ｒ１’ (wherein q1' is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1' is an integer of 0 to 2), or -Z １” -SiR ２２” ｑ１” R ２３” ｒ１” (wherein q1″ is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1″ is an integer of 0 to 2). Z １ , Z １’ , Z １” , R ２２ , R ２３ , R ２２’ , R ２３’ , R ２２” , and R ２３” has the same meaning as above.

[0174] In a preferred embodiment, in formula (S3), R ２１’ When present, at least one, preferably all, R ２１’ In the formula, q1″ is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0175] In a preferred embodiment, in formula (S3), R ２１ When present, at least one, preferably all, R ２１ In the formula (I), p1' is 0, and q1' is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0176] In a preferred embodiment, in formula (S3), R ａ１ When present, at least one, preferably all, R ａ１In the formula (I), p1 is 0, and q1 is an integer of 1 to 3, preferably 2 or 3, and 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 are each independently -Z ２ -CR ３１ ｐ２ R ３２ ｑ２ R ３３ ｒ２ is.

[0179] Z ２ are each independently a single bond, an oxygen atom, or a divalent organic group. ２ The structure written as follows is (CR ３１ ｐ２ R ３２ ｑ２ R ３３ ｒ２ )

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

[0181] Above Z ２ is preferably C １－６ Alkylene group, -(CH ２ ) ｚ５ -O-(CH ２ ) ｚ６ - (wherein z5 is an integer of 0 to 6, for example, an integer of 1 to 6, and z6 is an integer of 0 to 6, for example, an integer of 1 to 6), or - (CH ２ ) ｚ７ -phenylene-(CH ２ ) ｚ８ - (wherein z7 is an integer of 0 to 6, for example, an integer of 1 to 6, and z8 is an integer of 0 to 6, for example, an integer of 1 to 6). １－６ The alkylene group may be straight-chain or branched, but is preferably straight-chain. These groups may contain, for example, fluorine atoms, C １－６ Alkyl group, C ２－６ Alkenyl groups, and C２－６ It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0182] In a preferred embodiment, Z ２ is C １－６ Alkylene group or -(CH ２ ) ｚ７ -phenylene-(CH ２ ) ｚ８ -, preferably -phenylene-(CH ２ ) ｚ８ - is. Z ２ is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.

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

[0184] R ３１ are each independently -Z ２’ -CR ３２’ ｑ２’ R ３３’ ｒ２’ is.

[0185] Z ２’ are each independently a single bond, an oxygen atom, or a divalent organic group. ２’ The structure written as follows is (CR ３２’ ｑ２’ R ３３’ ｒ２’ )

[0186] Above Z ２’ is preferably C １－６ Alkylene group, -(CH ２ ) ｚ５’ -O-(CH ２ ) ｚ６’- (wherein z5' is an integer of 0 to 6, for example, an integer of 1 to 6, and z6' is an integer of 0 to 6, for example, an integer of 1 to 6), or - (CH ２ ) ｚ７’ -phenylene-(CH ２ ) ｚ８’ - (wherein z7' is an integer of 0 to 6, for example, an integer of 1 to 6, and z8' is an integer of 0 to 6, for example, an integer of 1 to 6). １－６ The alkylene group may be straight-chain or branched, but is preferably straight-chain. These groups may contain, for example, fluorine atoms, C １－６ Alkyl group, C ２－６ Alkenyl groups, and C ２－６ It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0187] In a preferred embodiment, Z ２’ is C １－６ Alkylene group or -(CH ２ ) ｚ７’ -phenylene-(CH ２ ) ｚ８’ -, preferably -phenylene-(CH ２ ) ｚ８’ - is. Z ２’ is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.

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

[0189] The above R ３２’ are each independently -Z ３ -SiR ３４ ｎ２ R ３５ ３－ｎ２ is.

[0190] Above Z３ are each independently a single bond, an oxygen atom, or a divalent organic group. ３ The structure written as ３４ ｎ２ R ３５ ３－ｎ２ )

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

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

[0193] Above Z ３ is preferably C １－６ Alkylene group, -(CH ２ ) ｚ５” -O-(CH ２ ) ｚ６” - (wherein z5" is an integer of 0 to 6, for example, an integer of 1 to 6, and z6" is an integer of 0 to 6, for example, an integer of 1 to 6), or - (CH ２ ) ｚ７” -phenylene-(CH ２ ) ｚ８” - (wherein z7" is an integer of 0 to 6, for example, an integer of 1 to 6, and z8" is an integer of 0 to 6, for example, an integer of 1 to 6). １－６ The alkylene group may be straight-chain or branched, but is preferably straight-chain. These groups may contain, for example, fluorine atoms, C １－６ Alkyl group, C ２－６ Alkenyl groups, and C ２－６ It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0194] In a preferred embodiment, Z ３ is C １－６ Alkylene group or -(CH ２ ) ｚ７” -phenylene-(CH ２ ) ｚ８” -, preferably -phenylene-(CH ２ ) ｚ８” - is. Z ３is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.

[0195] In another preferred embodiment, the Z ３ is C １－３ In one embodiment, Z is an alkylene group. ３ is -CH ２ CH ２ CH ２ In another embodiment, Z ３ is -CH ２ CH ２ -It can be.

[0196] The above R ３４ are each independently a hydroxyl group or a hydrolyzable group.

[0197] R ３４ are preferably each independently a hydrolyzable group.

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

[0199] The above R ３５ are each independently a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0200] The above R ３５ In the formula (I), the monovalent organic group is preferably C １－２０ alkyl group, more preferably C １－６ It is preferably an alkyl group, more preferably a methyl group.

[0201] In the above formula, n2 is (SiR ３４ ｎ２ R ３５ ３－ｎ２ ) units are each independently an integer of 0 to 3, provided that R Ｓｉ is a group represented by formula (S4), n2 is 1 to 3 in the terminal portion of formula (1) and formula (2) (SiR ３４ ｎ２ R ３５ ３－ｎ２ ) unit is present. That is, in such a terminal portion, all n2s do not become 0 at the same time. In other words, in the terminal portion of formula (1) and formula (2), there is at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

[0202] n2 is (SiR ３４ ｎ２ R ３５ ３－ｎ２ ) units are each independently an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0203] The above R ３３’ are each independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0204] The above R ３３’ In the formula (I), the monovalent organic group is preferably C １－２０ Alkyl group or -(C ｓ H ２ｓ ) ｔ１ -(O-C ｓ H ２ｓ ) ｔ２ H (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4; t1 is 1 or 0, preferably 0; t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), and more preferably C １－２０alkyl group, more preferably C １－６ An 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 C １－２０ alkyl group, more preferably C １－６ It is an alkyl group.

[0207] Each of the q2's is independently an integer of 0 to 3, and each of the r2's is independently an integer of 0 to 3. The sum of q2' and r2' is (CR ３２’ ｑ２’ R ３３’ ｒ２’ ) units, it is 3.

[0208] q2' is (CR ３２’ ｑ２’ R ３３’ ｒ２’ ) units are each independently an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0209] R ３２ are each independently -Z ３ -SiR ３４ ｎ２ R ３５ ３－ｎ２ This is -Z ３ -SiR ３４ ｎ２ R ３５ ３－ｎ２ is the above R ３２’ This has the same meaning as the description in

[0210] The above R ３３ are each independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

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

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

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

[0214] Each of the above p2's is independently an integer of 0 to 3, each of the q2's is independently an integer of 0 to 3, and each of the r2's is independently an integer of 0 to 3. The sum of p2, q2, and r2 is (CR ３１ ｐ２ R ３２ ｑ２ R ３３ ｒ２ ) units, it is 3.

[0215] In one embodiment, p2 is 0.

[0216] In one embodiment, p2 is (CR ３１ ｐ２ R ３２ ｑ２ R ３３ ｒ２ ) units may each independently 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 ) units are each independently an integer of 1 to 3, preferably an integer of 2 or 3, and more preferably 3.

[0218] In one embodiment, p2 is 0 and q2 is (CR ３１ ｐ２ R ３２ ｑ２ R ３３ ｒ２ ) units are each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.

[0219] The above R ｅ１ are each independently -Z ３ -SiR ３４ ｎ２ R ３５ ３－ｎ２ This is -Z ３ -SiR ３４ ｎ２ R ３５ ３－ｎ２ is the above R ３２’ This has the same meaning as the description in

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

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

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

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

[0224] Each of the k2's is independently an integer of 0 to 3, each of the l2's is independently an integer of 0 to 3, and each of the m2's is independently an integer of 0 to 3. The sum of k2, l2, and m2 is (CR ｄ１ ｋ２ R ｅ１ ｌ２ R ｆ１ ｍ２ ) units, it is 3.

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

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

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

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

[0229] In a preferred embodiment, in formula (S4), R ｅ１When present, at least one, preferably all, R ａ１ In the formula, n2 is an integer of 1 to 3, preferably 2 or 3, and 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 are each 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 meanings as above.

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

[0233] Above Z ４ are each independently a single bond, an oxygen atom, or a divalent organic group. ４ The structure written as １１ ｎ１ R １２ ３－ｎ１)

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

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

[0236] Above Z ４ is preferably C １－６ Alkylene group, -(CH ２ ) ｚ５” -O-(CH ２ ) ｚ６” - (wherein z5" is an integer of 0 to 6, for example, an integer of 1 to 6, and z6" is an integer of 0 to 6, for example, an integer of 1 to 6), or - (CH ２ ) ｚ７” -phenylene-(CH ２ ) ｚ８” - (wherein z7" is an integer of 0 to 6, for example, an integer of 1 to 6, and z8" is an integer of 0 to 6, for example, an integer of 1 to 6). １－６ The alkylene group may be straight-chain or branched, but is preferably straight-chain. These groups may contain, for example, fluorine atoms, C １－６ Alkyl group, C ２－６ Alkenyl groups, and C ２－６ It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0237] In a preferred embodiment, Z ４ is C １－６ Alkylene group or -(CH ２ ) ｚ７” -phenylene-(CH ２ ) ｚ８” -, preferably -phenylene-(CH ２ ) ｚ８” - is. Z ３ is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.

[0238] In another preferred embodiment, the Z ４ is C １－３ In one embodiment, Z is an alkylene group. ４ is -CH ２ CH２ CH ２ In another embodiment, Z ４ is -CH ２ CH ２ -It can be.

[0239] In one embodiment, R Ｓｉ is a group represented by formula (S2), (S3), (S4) or (S5): These compounds can form a surface treatment layer having high surface slip properties.

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

[0241] In one embodiment, R Ｓｉ is a group represented by formula (S3) or (S4). These compounds can have multiple hydrolyzable groups branched from one Si atom or C atom at one end, and therefore can form a surface treatment layer with even higher abrasion resistance.

[0242] In one embodiment, R Ｓｉ is a group represented by formula (S1).

[0243] In one embodiment, R Ｓｉ is a group represented by formula (S2).

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

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

[0246] In one embodiment, R Ｓｉ is a group represented by formula (S5).

[0247] In the above formulas (1) and (2), X Ａ is a fluoropolyether moiety (R ) that mainly provides water repellency and surface slipperiness. Ｆ１ and R Ｆ２ ) and the portion (RＳｉ ) and the linker. Ａ 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 the above formula (1), α is an integer of 1 to 9, and β is an integer of 1 to 9. These α and β are X Ａ The sum of α and β can vary depending on the valence of X Ａ For example, X Ａ When X is a decavalent organic group, the sum of α and β is 10, and for example, α can be 9 and β can be 1, α can be 5 and β can be 5, or α can be 1 and β can be 9. Ａ When is a divalent organic group, α and β are 1.

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

[0250] X Ａ are each independently a single bond or a divalent to decavalent organic group;

[0251] Above X Ａ The divalent to decavalent organic group in the formula (I) is preferably a divalent to octavalent organic group. In one embodiment, the divalent to decavalent organic group is preferably a divalent to tetravalent organic group, more preferably a divalent organic group. In another embodiment, the divalent to decavalent organic group is preferably a trivalent to octavalent organic group, more preferably a trivalent to hexavalent organic group.

[0252] In one embodiment, X Ａ represents a single bond or a divalent organic group, α is 1, and β is 1.

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

[0254] In one embodiment, X Ａ is a trivalent to hexavalent organic group, α is 1, and β is 2 to 5.

[0255] In one embodiment, X Ａ is a trivalent to hexavalent organic group, and γ is 2 to 5.

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

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

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

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

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

[0261] In one embodiment, X Ａ is, for example, a single bond or the following formula: -(R ５１ ) ｐ５ -(X ５１ ) ｑ５ - [In the formula: R ５１ is a single bond, -(CH ２ ) ｓ５ - or an o-, m- or p-phenylene group, preferably -(CH ２ ) ｓ５ -, s5 is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2; X ５１ is -(X ５２ ) ｌ５ represents -, and X ５２ each independently represents an —O—, —S—, o-, m-, or p-phenylene group, —C(O)O—, —Si(R ５３ ) ２ -, -(Si(R ５３ ) ２ O) ｍ５ -Si(R ５３ ) ２ --, --CONR ５４ --, --O-CONR５４ -, -NR ５４ - and - (CH ２ ) ｎ５ represents a group selected from the group consisting of -, ５３ are each independently a phenyl group, C １－６ Alkyl group or C １－６ represents an alkoxy group, preferably a phenyl group or C １－６ R is an alkyl group, more preferably a methyl group; ５４ are each independently a hydrogen atom, a phenyl group, or C １－６ represents an alkyl group (preferably a methyl group), m5 is, each independently an integer of 1 to 100, preferably an integer of 1 to 20, n5 is, each independently an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, l5 is, each independently an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, p5 is 0 or 1, q5 is 0 or 1, wherein at least one of p5 and q5 is 1, and the order of the repeating units enclosed in parentheses with p5 or q5 is arbitrary. Ａ (Typically X Ａ hydrogen atom) is a fluorine atom, C １－３ Alkyl group and C １－３ In a preferred embodiment, X Ａ is not substituted with these groups.

[0262] In a preferred embodiment, the X Ａ are each independently -(R ５１ ) ｐ５ -(X ５１ ) ｑ５ -R ５２ - is. R ５２ is a single bond, -(CH ２ ) ｔ５ - or an o-, m- or p-phenylene group, preferably -(CH ２ ) ｔ５t5 is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. ５２ (Typically R ５２ hydrogen atom) is a fluorine atom, C １－３ Alkyl group and C １－３ In a preferred embodiment, R ５６ is not substituted with these groups.

[0263] Preferably, the X Ａ are each independently a single bond, C １－２０ an alkylene group, —R ５１ -X ５３ -R ５２ - or -X ５４ -R ５２ - [wherein, R ５１ and R ５２ has the same meaning as above, and X ５３ -O-, -S-, -C(O)O-, -CONR ５４ -, -O-CONR ５４ -, -Si(R ５３ ) ２ -, -(Si(R ５３ ) ２ O) ｍ５ -Si(R ５３ ) ２ -, -O-(CH ２ ) u５ -(Si(R ５３ ) ２ O) ｍ５ -Si(R ５３ ) ２ -, -O-(CH ２ ) u５ -Si(R ５３ ) ２ —O—Si(R ５３ ) ２ -CH ２ CH ２ -Si(R ５３ ) ２ —O—Si(R ５３ ) ２ -, -O-(CH ２ ) u５ -Si(OCH３ ) ２ OSi(OCH ３ ) ２ -, -CONR ５４ - (CH ２ ) u５ -(Si(R ５３ ) ２ O) ｍ５ -Si(R ５３ ) ２ -, -CONR ５４ - (CH ２ ) u５ -N(R ５４ ) -, or -CONR ５４ -(o-, m- or p-phenylene)-Si(R ５３ ) ２ - (wherein, R ５３ , R ５４ and m5 are as defined above, and u5 is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3; ５４ is -S-, -C(O)O-, -CONR ５４ -, -O-CONR ５４ -, -CONR ５４ - (CH ２ ) u５ -(Si(R ５４ ) ２ O) ｍ５ -Si(R ５４ ) ２ -, -CONR ５４ - (CH ２ ) u５ -N(R ５４ ) -, or -CONR ５４ -(o-, m- or p-phenylene)-Si(R ５４ ) ２ - (wherein each symbol has the same meaning as above).

[0264] More preferably, the above X Ａ are each independently a single bond, C １－２０ an alkylene group, —(CH ２ ) ｓ５ -X ５３ -, -(CH ２ ) ｓ５ -X ５３- (CH ２ ) ｔ５ - -X ５４ - or -X ５４ - (CH ２ ) ｔ５ - [wherein, X ５３ , X ５４ , s5 and t5 have the same meanings as above.]

[0265] More preferably, the above X Ａ are each independently a single bond, C １－２０ an alkylene group, —(CH ２ ) ｓ５ -X ５３ - (CH ２ ) ｔ５ - or -X ５４ - (CH ２ ) ｔ５ wherein each symbol has the same meaning as defined above.

[0266] In a preferred embodiment, the X Ａ are each independently a single bond C １－２０ an alkylene group, —(CH ２ ) ｓ５ -X ５３ - or -(CH ２ ) ｓ５ -X ５３ - (CH ２ ) ｔ５ - [wherein, X ５３ is -O-, -CONR ５４ -, or -O-CONR ５４ - and R ５４ are each independently a hydrogen atom, a phenyl group, or C １－６ represents an alkyl group, s5 is an integer of 1 to 20, and t5 is an integer of 1 to 20.

[0267] In a preferred embodiment, the X Ａ are each independently -(CH ２ ) ｓ５ -O-(CH ２ ) ｔ５ --CONR ５４ - (CH ２ ) ｔ５ - [wherein, R５４ are each independently a hydrogen atom, a phenyl group, or C １－６ represents an alkyl group, s5 is an integer of 1 to 20, and t5 is an integer of 1 to 20.

[0268] In one embodiment, the X Ａ are each independently a single bond, C １－２０ an alkylene group, —(CH ２ ) ｓ５ -O-(CH ２ ) ｔ５ -, -(CH ２ ) ｓ５ -(Si(R ５３ ) ２ O) ｍ５ -Si(R ５３ ) ２ - (CH ２ ) ｔ５ -, -(CH ２ ) ｓ５ -O-(CH ２ ) u５ -(Si(R ５３ ) ２ O) ｍ５ -Si(R ５３ ) ２ - (CH ２ ) ｔ５ - or -(CH ２ ) ｓ５ -O-(CH ２ ) ｔ５ -Si(R ５３ ) ２ - (CH ２ ) u５ -Si(R ５３ ) ２ -(C v H ２v ) - [wherein, R ５３ , m5, s5, t5 and u5 are as defined above, and v5 is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 or 3.]

[0269] In the above formula, -(C v H ２v )- may be a straight chain or a branched chain, for example, -CH ２ CH ２ -, -CH ２CH ２ CH ２ -, -CH(CH ３ ) -, -CH(CH ３ ) CH ２ -It can be.

[0270] Above X Ａ are each independently a fluorine atom, C １－３ Alkyl group and C １－３ Fluoroalkyl groups (preferably C １－３ In one embodiment, X may be substituted with one or more substituents selected from the group consisting of alkyl, aryl, aryls ... Ａ is non-substituted.

[0271] In addition, the above X Ａ The left side of each equation is R Ｆ１ or R Ｆ２ and the right side is R Ｓｉ Combine with.

[0272] In one embodiment, X Ａ are each independently —O—C １－６ It may be other than an alkylene group.

[0273] In another embodiment, X Ａ Examples of the group include the following: [In the formula, R ４１ are each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or C １－６ an alkoxy group, preferably a methyl group; D is —CH ２ O (CH ２ ) ２ -, -CH ２ O (CH ２ ) ３ -, -CF ２ O (CH ２ ) ３ -, -(CH ２ ) ２ -, -(CH ２ ) ３ -, -(CH ２ )4-, -CONH-(CH ２ ) ３ -, -CON(CH ３ )-(CH２ ) ３ -, -CON(Ph)-(CH ２ ) ３ - (wherein Ph means phenyl), and (In the formula, R ４２ are each independently a hydrogen atom, C １－６ or an alkyl group of C １－６ E represents an alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group; ２ ) ｎ - (n is an integer of 2 to 6), and D is R of the molecular main chain. Ｆ１ or R Ｆ２ and E is R Ｓｉ binds to.]

[0274] Above X Ａ Specific examples of include: a single bond, —CH ２ OCH ２ -, -CH ２ O (CH ２ ) ２ -, -CH ２ O (CH ２ ) ３ -, -CH ２ O (CH ２ ) ４ -, -CH ２ O (CH ２ ) ５ -, -CH ２ O (CH ２ ) ６ -, -CH ２ O (CH ２ ) ３ Si(CH ３ ) ２ OSi(CH ３ ) ２ (CH ２ ) ２ -, -CH ２ O (CH ２ ) ３ Si(CH ３ ) ２ OSi(CH ３ ) ２ OSi(CH ３ ) ２ (CH ２) ２ -CH ２ O(CH) ２ ) ３ Si(CH) ３ ) ２ O(Si(CH) ３ ) ２ O) ２ Si(CH) ３ ) ２ (CH) ２ ) ２ -CH ２ O(CH) ２ ) ３ Si(CH) ３ ) ２ O(Si(CH) ３ ) ２ O) ３ Si(CH) ３ ) ２ (CH) ２ ) ２ -CH ２ O(CH) ２ ) ３ Si(CH) ３ ) ２ O(Si(CH) ３ ) ２ O) １０ Si(CH) ３ ) ２ (CH) ２ ) ２ -CH ２ O(CH) ２ ) ３ Si(CH) ３ ) ２ O(Si(CH) ３ ) ２ O) ２０ Si(CH) ３ ) ２ (CH) ２ ) ２ -CH ２ OCF ２ CHFOCF ２ -CH ２ OCF ２ CHFOCF ２ CF ２ -CH ２ OCF ２ CHFOCF ２ CF ２ CF ２ -CH２ OCH ２ CF ２ CF ２ OCF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF ２ CF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF ２ CF ２ CF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF(CF ３ )CF ２ OCF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF(CF ３ )CF ２ OCF ２ CF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF(CF ３ )CF ２ OCF ２ CF ２ CF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF ２ CF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF ２ CF ２ CF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF(CF ３ )CF２ OCF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF(CF ３ )CF ２ OCF ２ CF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF(CF ３ )CF ２ OCF ２ CF ２ CF ２ -、 -CH ２ OCF ２ CHFOCF ２ CF ２ CF ２ -C(O)NH-CH ２ -、 -CH ２ OCH ２ (CH) ２ ) ７ CH ２ Si(OCH ３ ) ２ OSi (OCH) ３ ) ２ (CH) ２ ) ２ Si(OCH ３ ) ２ OSi (OCH) ３ ) ２ (CH) ２ ) ２ -、 -CH ２ OCH ２ CH ２ CH ２ Si(OCH ３ ) ２ OSi (OCH) ３ ) ２ (CH) ２ ) ３ -、 -CH ２ OCH ２ CH ２ CH ２ Si(OCH ２ CH ３ ) ２ OSi (OCH) ２ CH ３ ) ２ (CH) ２) ３ -CH ２ OCH ２ CH ２ CH ２ Si(OCH) ３ ) ２ OSi(OCH) ３ ) ２ (CH) ２ ) ２ -CH ２ OCH ２ CH ２ CH ２ Si(OCH) ２ CH ３ ) ２ OSi(OCH) ２ CH ３ ) ２ (CH) ２ ) ２ -、 -(CH ２ ) ２ -Si(CH) ３ ) ２ -(CH) ２ ) ２ -CH ２ -、 -(CH ２ ) ２ -、 -(CH ２ ) ３ -、 -(CH ２ ) ４ -、 -(CH ２ ) ５ -、 -(CH ２ ) ６ -、 -CO-、 -CONH-、 -CONH-CH ２ -, -CONH-(CH) ２ ) ２ -, -CONH-(CH) ２ ) ３ -, -CONH-(CH) ２ ) ４ -, -CONH-(CH) ２ ) ５ -, -CONH-(CH) ２ ) ６ - -CON(CH) ３ )-CH ２ - -CON(CH) ３ ()-(CH ２ ) ２ - -CON(CH)３ )-(CH ２ ) ３ -, -CON(CH ３ )-(CH ２ ) ４ -, -CON(CH ３ )-(CH ２ ) ５ -, -CON(CH ３ )-(CH ２ ) ６ -, -CON(Ph)-CH ２ -(wherein Ph means phenyl), -CON(Ph)-(CH ２ ) ２ -(wherein Ph means phenyl), -CON(Ph)-(CH ２ ) ３ -(wherein Ph means phenyl), -CON(Ph)-(CH ２ ) ４ -(wherein Ph means phenyl), -CON(Ph)-(CH ２ ) ５ -(wherein Ph means phenyl), -CON(Ph)-(CH ２ ) ６ - (wherein Ph means phenyl), -CONH-(CH ２ ) ２ NH (CH ２ ) ３ -, -CONH-(CH ２ ) ６ NH (CH ２ ) ３ -, -CH ２ O-CONH-(CH ２ ) ３ -, -CH ２ O-CONH-(CH ２ ) ６ -, -S-(CH ２ ) ３ -, -(CH ２ ) ２ S (CH ２ ) ３ -, -CONH-(CH ２ ) ３ Si(CH ３ ) ２ OSi(CH ３ )２ (CH) ２ ) ２ -, -CONH-(CH) ２ ) ３ Si(CH) ３ ) ２ OSi(CH) ３ ) ２ OSi(CH) ３ ) ２ (CH) ２ ) ２ -, -CONH-(CH) ２ ) ３ Si(CH) ３ ) ２ O(Si(CH) ３ ) ２ O) ２ Si(CH) ３ ) ２ (CH) ２ ) ２ -, -CONH-(CH) ２ ) ３ Si(CH) ３ ) ２ O(Si(CH) ３ ) ２ O) ３ Si(CH) ３ ) ２ (CH) ２ ) ２ -, -CONH-(CH) ２ ) ３ Si(CH) ３ ) ２ O(Si(CH) ３ ) ２ O) １０ Si(CH) ３ ) ２ (CH) ２ ) ２ -, -CONH-(CH) ２ ) ３ Si(CH) ３ ) ２ O(Si(CH) ３ ) ２ O) ２０ Si(CH) ３ ) ２ (CH) ２ ) ２ -、 -C(O)O-(CH ２ ) ３ -、 -C(O)O-(CH ２) ６ -, -CH ２ -O-(CH ２ ) ３ -Si(CH ３ ) ２ - (CH ２ ) ２ -Si(CH ３ ) ２ - (CH ２ ) ２ -, -CH ２ -O-(CH ２ ) ３ -Si(CH ３ ) ２ - (CH ２ ) ２ -Si(CH ３ ) ２ -CH(CH ３ ) -, -CH ２ -O-(CH ２ ) ３ -Si(CH ３ ) ２ - (CH ２ ) ２ -Si(CH ３ ) ２ - (CH ２ ) ３ -, -CH ２ -O-(CH ２ ) ３ -Si(CH ３ ) ２ - (CH ２ ) ２ -Si(CH ３ ) ２ -CH(CH ３ )-CH ２ -, -OCH ２ -, -O(CH ２ ) ３ -, -OCFHCF ２ -, Examples include:

[0275] In yet another embodiment, X Ａ are each independently represented by the formula: -(R １６ ) ｘ１ -(CFR １７ ) ｙ１ - (CH ２ ) ｚ１In the formula, x1, y1, and z1 each independently represent an integer of 0 to 10, the sum of x1, y1, and z1 is 1 or more, and the order of the repeating units enclosed in parentheses in the formula is arbitrary.

[0276] In the above formula, R １６ are each independently an oxygen atom, phenylene, carbazolylene, or —NR １８ - (wherein, R １８ represents a hydrogen atom or an organic group) or a divalent organic group. １８ is an oxygen atom or a divalent polar group.

[0277] The "divalent polar group" is not particularly limited, but examples thereof include -C(O)-, -C(=NR １９ )-, and -C(O)NR １９ - (wherein R １９ represents a hydrogen atom or a lower alkyl group). The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, or n-propyl, which may be substituted with one or more fluorine atoms.

[0278] In the above formula, R １７ are each 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, a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.

[0279] In yet another embodiment, X Ａ Examples of include the following groups: [In the formula, R ４１ are each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or C １－６ The alkoxy group is preferably a methyl group; Ａ In the group, any number of T's may be R Ｆ１ or R Ｆ２ The following groups are attached to:２ O (CH ２ ) ２ -, -CH ２ O (CH ２ ) ３ -, -CF ２ O (CH ２ ) ３ -, -(CH ２ ) ２ -, -(CH ２ ) ３ -, -(CH ２ )4-, -CONH-(CH ２ ) ３ -, -CON(CH ３ )-(CH ２ ) ３ -, -CON(Ph)-(CH ２ ) ３ - (wherein Ph means phenyl), or [In the formula, R ４２ are each independently a hydrogen atom, C １－６ or an alkyl group of C １－６ represents an alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group.], and some of the other Ts are R Ｓｉ and if present, the remaining Ts are each independently a methyl group, a phenyl group, C １－６ It is an alkoxy group, a radical scavenger 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, and examples thereof include residues of benzophenones, benzotriazoles, benzoic acid esters, phenyl salicylates, crotonic acids, malonic acid esters, organoacrylates, hindered amines, hindered phenols, and triazines.

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

[0282] In a preferred embodiment, preferred radical scavenging groups or ultraviolet absorbing groups include: Examples include:

[0283] In this embodiment, X Ａ may each independently be a trivalent to decavalent organic group.

[0284] In yet another embodiment, X Ａ Examples of include the following groups: [In the formula, R ２５ , R ２６ and R ２７ are each independently a divalent to hexavalent organic group, and R ２５ is at least one R Ｆ１ and bonded to R ２６ and R ２７ Each of the groups is at least one R Ｓｉ binds to.]

[0285] In one embodiment, the R ２５ is a single bond, C １－２０ Alkylene group, C ３－２０ Cycloalkylene group, C ５－２０ arylene group, —R ５７ -X ５８ -R ５９ -, -X ５８ -R ５９ - or -R ５７ -X ５８ -. ５７ and R ５９ are each independently a single bond, C １－２０ Alkylene group, C ３－２０ a cycloalkylene group, or C ５－２０ The X is an arylene group. ５８ is —O—, —S—, —CO—, —O—CO— or —COO—.

[0286] In one embodiment, the R ２６ and R ２７ are each independently a hydrocarbon or a group having at least one atom selected from N, O and S at the end or in the main chain of the hydrocarbon, and preferably C １－６ alkyl group, -R３６ -R ３７ -R ３６ -, -R ３６ -CHR ３８ ２ -, etc. Here, R ３６ are each independently a single bond or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. ３７ is N, O or S, preferably N or O. ３８ is -R ４５ -R ４６ -R ４５ -, -R ４６ -R ４５ -or-R ４５ -R ４６ -. Here, R ４５ are each independently an alkyl group having 1 to 6 carbon atoms. ４６ is N, O or S, preferably O.

[0287] In this embodiment, X Ａ may each independently be a trivalent to decavalent organic group.

[0288] In yet another embodiment, X Ａ For example, the following: [In the formula, X ａ is a single bond or a divalent organic group.

[0289] Above X ａ is a single bond or a divalent linking group directly bonded to the isocyanuric ring. ａ is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond, and more preferably a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent hydrocarbon group having 1 to 10 carbon atoms and containing 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 following formula: -(CX １２１ X １２２ ) ｘ１ -(Xａ１ ) ｙ１ - (CX １２３ X １２４ ) ｚ１ - (wherein, X １２１ ~X １２４ are each independently H, F, OH, or —OSi(OR １２１ ) ３ (wherein three R １２１ are each independently an alkyl group having 1 to 4 carbon atoms, and ａ１ is -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, or -NHC(=O)NH- (the left side of each bond is CX １２１ X １２２ ), x1 is an integer of 0 to 10, y1 is 0 or 1, and z1 is an integer of 1 to 10.

[0291] Above X ａ１ is preferably —O— or —C(═O)O—.

[0292] Above X ａ The following formula: -(CF ２ ) ｍ１１ - (CH ２ ) ｍ１２ -O-(CH ２ ) ｍ１３ - (wherein m11 is an integer of 1 to 3, m12 is an integer of 1 to 3, and m13 is an integer of 1 to 3), a group represented by -(CF ２ ) ｍ１４ - (CH ２ ) ｍ１５ -O-CH ２ CH(OH)-(CH ２ ) ｍ１６ - (wherein m14 is an integer of 1 to 3, m15 is an integer of 1 to 3, and m16 is an integer of 1 to 3), a group represented by -(CF ２ ) ｍ１７ - (CH ２ ) ｍ１８ - (wherein m17 is an integer of 1 to 3, and m18 is an integer of 1 to 3), a group represented by -(CF ２ )ｍ１９ - (CH ２ ) ｍ２０ -O-CH ２ CH(OSi(OCH ３ ) ３ )-(CH ２ ) ｍ２１ - (wherein m19 is an integer of 1 to 3, m20 is an integer of 1 to 3, and m21 is an integer of 1 to 3), or -(CH ２ ) ｍ２２ A group represented by the formula: - (wherein m22 is an integer of 1 to 3) is particularly preferred.

[0293] Above X ａ is not particularly limited, but specifically includes -CH ２ -, -C ２ H ４ -, -C ３ H ６ -, -C ４ H ８ -, -C ４ H ８ -O-CH ２ -, -CO-O-CH ２ -CH(OH)-CH ２ -, - (CF ２ ) ｎ５ -(n5 is an integer from 0 to 4), -(CF ２ ) ｎ５ - (CH ２ ) ｍ５ -(n5 and m5 each independently represents an integer of 0 to 4), -CF ２ CF ２ CH ２ OCH ２ CH(OH)CH ２ -, -CF ２ CF ２ CH ２ OCH ２ CH(OSi(OCH ３ ) ３ ) CH ２ - etc.

[0294] In this embodiment, X Ａ may each independently be a divalent or trivalent organic group.

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

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

[0297] In one embodiment, the 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 mass%, more preferably 1.0 to 30.0 mass%, even more preferably 5.0 to 25.0 mass%, and particularly preferably 10.0 to 20.0 mass%, based on the total mass of the surface treatment agent.

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

[0300] In one embodiment, the surface treatment agent may contain at least one of the composition and a compound formed by 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 condensation of at least a portion of the silane compound.

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

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

[0303] In one embodiment, the surface treatment agent is R ９０ Further included are compounds represented by —OH. ９０ is a monovalent organic group, preferably C １－２０ Alkyl group or C ３－２０ The alkylene group may be substituted with one or more substituents. Examples of the substituents include a hydroxyl group, -OR ９１ (where R ９１ is C １－１０ Alkyl group, preferably C １－３ alkyl groups, such as methyl groups.

[0304] In one embodiment, the surface treatment agent is R ８１ OR ８２ , R ８３ ｎ８ C ６ H 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 formula R ８１ ~R ８９ are each independently a monovalent organic group having 1 to 10 carbon atoms, m8 is an integer of 1 to 6, m9 is an integer of 3 to 8, and n8 is an integer of 0 to 6.

[0305] The monovalent organic group having 1 to 10 carbon atoms may be linear or branched, and may further 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 a hydrocarbon group which is not substituted with a halogen.

[0309] In one embodiment, the hydrocarbon group is linear.

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

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

[0312] In one embodiment, the solvent is R ８１ OR ８２ is.

[0313] R ８１ and R ８２ are each independently preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably C １－６ or an alkyl group of C ５－８ It can be a cycloalkyl group of the formula:

[0314] In one embodiment, the solvent is R ８３ ｎ８ C ６ H ６－ｎ８ is.

[0315] C ６ H ６－ｎ８ is an n-octavalent benzene ring. That is, R ８３ ｎ８ C ６ H ６－ｎ８ is n8 R ８３ is benzene substituted with

[0316] R ８３ are each independently a halogen or a C optionally substituted by a halogen. １－６ The alkyl group may be:

[0317] n8 is preferably an integer of 1 to 3.

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

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

[0320] R ８４ ~R ８９ are each independently a hydrogen atom or C １－６ alkyl group, preferably C １－６ alkyl groups of the formula C １－３ The alkyl group is preferably a methyl group.

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

[0322] m9 is preferably an integer of 3 to 6, more preferably an integer of 3 to 5.

[0323] In one embodiment, the solvent may be, for example, an aliphatic hydrocarbon such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, or mineral spirit; an aromatic hydrocarbon such as benzene, toluene, xylene, naphthalene, or solvent naphtha; or an alkyl ester such as 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 acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl amino ketone, 2-heptanone; ethyl cellosolve, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether ... 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; diethylene glycol monoethyl ether acetate;Polyfluoroaromatic hydrocarbons (e.g., 1,3-bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C; ６ F １３ CH ２ CH ３ (For example, Asahiklin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), C ６ F １３ H (for example, Asahiklin (registered trademark) AC-2000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeorora (registered trademark) H manufactured by Zeon Corporation); fluorine-containing 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; CF ３ CH ２ OH, CF ３ CF ２ CH ２ OH, (CF ３ ) ２ fluorine-containing alcohols such as CHOH; hydrofluoroethers (HFEs) (for example, perfluoropropyl methyl ether (C ３ F ７ OCH ３ ) (e.g., Novec (trademark) 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C ４ F ９ OCH ３ ) (e.g., Novec (trademark) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C ４ F ９ O.C. ２ H ５ ) (e.g., Novec (trademark) 7200 manufactured by Sumitomo 3M Limited), perfluorohexyl methyl ether (C ２ F ５ CF (OCH ３ ) C ３ F ７) (e.g., Novec™ 7300 manufactured by Sumitomo 3M Limited) (the perfluoroalkyl group and the alkyl group may be linear or branched), or CF ３ CH ２ OCF ２ CHF ２ (e.g., Asahiklin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.), hydrofluoroolefins; CF ３ CH═CHCl (e.g., CELEFIN® 1233Z manufactured by Central Glass Co., Ltd.), CHF ２Examples of suitable solvents include ethers such as CF═CHCl (for example, AMOLEA (registered trademark) 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 sulfoxide. Alternatively, examples include 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 acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, 2- Preferred are ethyl hydroxyisobutyrate propylene glycol monomethyl ether, 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.

[0324] The silicone oil is not particularly limited, but examples thereof include silicone oils represented by the following general formula (3a): １０１ａ -(SiR １０３ａ ２-O) ａ１ -SiR １０３ａ ２ -R １０１ａ ...(3a) [wherein: R １０１ａ are each independently a hydrogen atom or a hydrocarbon group, １０３ａ are each independently a hydrogen atom or a hydrocarbon group, and a1 is 2 to 3,000.

[0325] The above R １０３ａ are each independently a hydrogen atom or a hydrocarbon group. Such hydrocarbon groups may be substituted.

[0326] R １０３ａ are each independently preferably an unsubstituted hydrocarbon group or a hydrocarbon group substituted with a halogen atom.

[0327] R １０３ａ are each independently preferably C optionally substituted by a halogen atom. １－６ an alkyl group or an aryl group, more preferably C １－６ It is an alkyl group or an aryl group.

[0328] Above C １－６ The alkyl group may be a straight chain or a branched chain, but is preferably a straight chain. １－６ The alkyl group is preferably C １－３ It is preferably an alkyl group, more preferably a methyl group.

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

[0330] In one embodiment, R １０３ａ are each independently C １－６ Alkyl group, preferably C １－３ It is preferably an alkyl group, more preferably a methyl group.

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

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

[0333] The above R １０１ａ are each independently a hydrogen atom or a hydrocarbon group, and ３ａ It has the same meaning as:

[0334] R １０１ａ are each independently preferably C optionally substituted by a halogen atom. １－６ an alkyl group or an aryl group, more preferably C １－６ It is an alkyl group or an aryl group.

[0335] In one embodiment, R １０１ａ are each independently C １－６ Alkyl group, preferably C １－３ It is preferably an alkyl group, more preferably a methyl group.

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

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

[0338] The above a1 is 2 to 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 be preferably 5 to 1000, more preferably 10 to 500, even more preferably 15 to 200, and even more preferably 15 to 150.

[0340] Another silicone oil is the following (3b): １０１ａ -R ＳＯ２ -R １０３ａ ...(3b) [wherein: R １０１ａ are each independently a hydrocarbon group; R １０３ａ are each independently a hydrocarbon group; R ＳＯ２ is -R Ｓ -SiR ５ ２ - and RＳ and R ５ has the same meaning as above.]

[0341] The 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 silicone oil include -(SiR ３ａ ２ -O) ａ１ Linear or cyclic silicone oils in which a1 is 30 or less can be used. The linear silicone oils may be so-called straight silicone oils or 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, or the like. Examples of cyclic silicone oils include cyclic dimethylsiloxane oil.

[0343] The silicone oil may be contained 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, relative to the surface treatment agent.

[0344] In the surface treatment agent, the silicone oil may be contained 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, relative to a total of 100 parts by mass of the compounds contained in the composition of the present disclosure (if there are two or more types, the total of these, same applies hereinafter).

[0345] The silicone oil contributes to improving the surface slipperiness of the surface treatment layer.

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

[0347] Examples of the catalyst 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 an unshared electron pair in the molecular structure, or nitrogen-containing compounds (e.g., sulfoxide compounds, aliphatic amine compounds, aromatic amine compounds, phosphoric acid amide compounds, amide compounds, urea compounds), etc.

[0348] Examples of the aliphatic amine compounds include diethylamine, triethylamine, etc. Examples of the aromatic amine compounds include aniline, pyridine, etc.

[0349] In a preferred embodiment, the transition metal is contained as a transition metal compound represented by M-R (wherein M is a transition metal atom and R is a hydrolyzable group). By using a transition metal compound in which a transition metal is bonded to a hydrolyzable group, the transition metal atom can be more efficiently contained in the surface treatment layer, and the friction durability and chemical resistance of the surface treatment layer can be further improved.

[0350] The hydrolyzable group means a group that can undergo a hydrolysis reaction, similar to the hydrolyzable group in the above-mentioned compound, that is, a group that can be separated from a transition metal atom by a hydrolysis reaction. Examples of the hydrolyzable group include -OR ｍ , -OCOR ｍ , —O—N═CR ｍ ２ , -NR ｍ ２, -NHR ｍ , —NCO, halogen (wherein R ｍ is a substituted or unsubstituted C １－４ (representing an alkyl group) and the like.

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

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

[0353] In another embodiment, the hydrolyzable group may be different from the hydrolyzable group contained in the compound. By making the hydrolyzable groups in the compound and the transition metal compound different, the hydrolysis reactivity 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 (In the formula, R ｍ is a substituted or unsubstituted C １－４ is an alkyl group.), and preferably Ta(OCH ２ CH ３ ) ５ , or Si(OR ｍ ) １－ｍ１ R ｍ’ ｍ１ (In the formula, R ｍ is a substituted or unsubstituted C １－４ is an alkyl group, and R ｍ’ is C １－４is an alkyl group, and m1 is 0 or 1.), and preferably tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetraisopropoxysilane, dimethyldiethoxysilane, or dimethyldimethoxysilane.

[0356] The catalyst may be contained in an amount of, for example, 0.0002% by mass or more relative to the entire surface treatment agent (coating liquid). The catalyst is preferably contained in an amount of 0.02% by mass or more, and more preferably 0.04% by mass or more, relative to the entire surface treatment agent (coating liquid). The catalyst may be contained in an amount of, for example, 10% by mass or less, and particularly 1% by mass or less, relative to the entire surface treatment agent (coating liquid). The catalyst contained in the surface treatment agent at the above-mentioned concentration 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, based on 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 present disclosure, and promotes the formation of the layer formed by the composition of the present disclosure.

[0359] In addition to the above, other components include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane, and the like.

[0360] In addition to the above components, 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 dry coating, preferably vacuum deposition.

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

[0363] The surface treatment agent can be impregnated into a porous material, such as a porous ceramic material or a metal fiber, such as a flocculated steel wool, to form pellets, which can be used for vacuum deposition, for example.

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

[0365] The silicon oxide layer (B) is formed on the surface of the substrate (A), and then a water- and oil-repellent layer (C) formed from the surface treatment agent is formed on the silicon oxide layer (B), and this layer is post-treated as necessary to form the water- and oil-repellent layer (C).

[0366] The water-repellent layer (C) can be formed by applying the surface treatment agent to the surface of the silicon oxide layer (B) so as to coat the surface. The coating method is not particularly limited. For example, a wet coating method or a dry coating method can be used.

[0367] Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, wipe coating, squeegee coating, die coating, ink jet, casting, Langmuir-Blodgett coating, 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 beam, high frequency heating using microwaves, etc., ion beam, and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.

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

[0370] When using the wet coating method, the surface treatment agent of the present disclosure can be diluted with a solvent and then applied to the surface of a substrate. 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, mineral spirits, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, solvent naphtha, etc.; methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, carbohydrate acetate, etc. Esters such as ethanol, 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, methyl amino ketone, and 2-heptanone; ethyl cellosolve, methyl cellosol glycol ethers such as 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 ethers; 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., C; ６ F １３ CH ２ CH ３ (For example, Asahiklin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), C ６ F １３ H (for example, Asahiklin (registered trademark) AC-2000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeorora (registered trademark) H manufactured by Zeon Corporation); fluorine-containing 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; CF ３ CH ２ OH, CF ３ CF ２ CH ２ OH, (CF ３ ) ２ fluorine-containing alcohols such as CHOH; hydrofluoroethers (HFEs) (for example, perfluoropropyl methyl ether (C ３ F ７ OCH ３ ) (e.g., Novec (trademark) 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C ４ F ９ OCH ３ ) (e.g., Novec (trademark) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C ４ F ９ O.C. ２ H ５ ) (e.g., Novec (trademark) 7200 manufactured by Sumitomo 3M Limited), perfluorohexyl methyl ether (C ２ F ５ CF (OCH３ ) C ３ F ７ ) (e.g., Novec™ 7300 manufactured by Sumitomo 3M Limited) (the perfluoroalkyl group and the alkyl group may be linear or branched), or CF ３ CH ２ OCF ２ CHF ２ (e.g., Asahiklin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.), hydrofluoroolefins; CF ３ CH═CHCl (e.g., CELEFIN® 1233Z manufactured by Central Glass Co., Ltd.), CHF ２Examples of suitable solvents include ethers such as CF═CHCl (for example, AMOLEA (registered trademark) 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 sulfoxide. Alternatively, mixed solvents of two or more of these solvents may be used. 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 acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, 2- Preferred are ethyl hydroxyisobutyrate propylene glycol monomethyl ether, 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.

[0371] In one embodiment, when using the wet coating method, the solvent is, for example, R ９０ A compound represented by —OH can be used. ９０is a monovalent organic group, preferably C １－２０ Alkyl group or C ３－２０ The alkylene group may be substituted with one or more substituents. Examples of the substituents include a hydroxyl group, -OR ９１ (where R ９１ is C １－１０ Alkyl group, preferably C １－３ alkyl groups, such as methyl groups.

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

[0373] The layer formation of the surface treatment agent is preferably carried out so that the surface treatment agent is present in the layer together with a catalyst for hydrolysis and dehydration condensation. Conveniently, in the case of a wet coating method, the surface treatment agent may be diluted with a solvent, and then a catalyst may be added to the diluted solution of the surface treatment agent immediately before application to the substrate surface. In the case of a dry coating method, the surface treatment agent to which the catalyst has been added may be directly vapor-deposited (usually, vacuum vapor-deposited), or a metal porous body such as iron or copper may be vapor-deposited (usually, vacuum vapor-deposited) using a pellet-shaped material impregnated with the surface treatment agent of the present disclosure to which the catalyst has been added.

[0374] The catalyst may be any appropriate acid or base, transition metal (e.g., Ti, Ni, Sn, Zr, Al, B, etc.), sulfur-containing compound having an unshared electron pair in its molecular structure, or nitrogen-containing compound (e.g., sulfoxide compound, aliphatic amine compound, aromatic amine compound, phosphoric acid amide compound, amide compound, urea compound), etc. Examples of acid catalysts that can be used include acetic acid, formic acid, trifluoroacetic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, etc. Examples of base catalysts that can be used 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 described above.

[0375] The water- and oil-repellent layer (C) included in the article of the present disclosure can have high durability. In addition to high durability, the water- and oil-repellent layer (C) can have water repellency, oil repellency, antifouling properties (for example, preventing adhesion of stains such as fingerprints), waterproof properties (preventing water penetration into electronic components, etc.), surface slipperiness (or lubricity, for example, ease of wiping off stains such as fingerprints and excellent tactile feel to the fingers), chemical resistance, etc., depending on the composition of the surface treatment agent used, and can be suitably used as a functional thin film.

[0376] Therefore, the present disclosure further relates to an optical material having the above-mentioned water- and oil-repellent layer (C) as the outermost layer.

[0377] Preferred examples of the optical material include optical materials relating to displays and the like, such as those exemplified below, as well as a wide variety of other optical materials: for example, displays such as cathode ray tubes (CRTs; for example, personal computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, vacuum fluorescent displays (VFDs), and field emission displays (FEDs), or protective plates for such displays, or displays whose surfaces have been treated with an anti-reflection film.

[0378] The article of the present disclosure may be, but is not particularly limited to, an optical member. Examples of optical members include lenses for eyeglasses and the like; front protective plates, anti-reflection plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and personal digital assistants; disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; optical fibers; and the display surfaces of watches and clocks.

[0379] The article of the present disclosure may also be a medical device or medical material. The article having a layer obtained by the present disclosure may also be an automobile interior or exterior component. 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- and oil-repellent layer (C) is not particularly limited. In the case of optical members, the thickness of the layer may be, for example, in the range of 1 to 50 nm, preferably 1 to 30 nm, and more preferably 1 to 15 nm, from the viewpoints of optical performance, abrasion resistance, and antifouling properties.

[0381] An X-ray photoelectron spectroscopy (XPS) device, such as a PHI5000 VersaProbe II manufactured by ULVAC-PHI, can be used to measure the atomic composition and atomic ratio of the water- and oil-repellent layer (C). Measurement conditions for XPS analysis include a monochromated AlKα X-ray source at 25 W, a photoelectron detection area of ​​1400 μm × 300 μm, a photoelectron detection angle in the range of 20 to 90 degrees (e.g., 20, 45, or 90 degrees), and a pass energy of 23.5 eV. Gas cluster ion beams, Ar ions, or the like can be used for sputtering. Using the above device 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 compositions of the water- and oil-repellent layer (C) and the silicon oxide layer (B).

[0382] Depth analysis can also be performed. Measurement conditions for XPS analysis include using a monochromated AlKα ray at 25 W as the X-ray source, a photoelectron detection area of ​​1400 μm × 300 μm, a photoelectron detection angle in the range of 20 to 90 degrees (e.g., 20, 45, or 90 degrees), and a pass energy of 23.5 eV. Ar ions, gas cluster ions, or C ions can be used as sputtering ions. Sputtering can be performed by etching 1 to 100 nm, and the composition of the coating film at each etching depth can be obtained.

[0383] The detection depth can be adjusted appropriately by adjusting the photoelectron detection angle in the XPS analysis. For example, a shallow angle close to 20 degrees can achieve a detection depth of about 3 nm, while a deep angle close to 90 degrees can achieve a detection depth of about 10-odd nm.

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

[0385] The present invention will be explained in more detail with reference to the following examples, but the present invention is not limited to these examples.

[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. 1.04 g of a 1 M aqueous solution of p-toluenesulfonic acid and 87.7 mg of sodium p-toluenesulfonate 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 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. 1.73 g of 0.01 M aqueous nitric acid solution and 64.0 mg of sodium nitrate 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 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. 0.69 g of 0.01 M hydrochloric acid and 44.0 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, 2.75 g of ethanol, and 2.00 g of ion-exchanged 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. 0.35 g of 0.01 M hydrochloric acid and 44.0 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, 2.75 g of ethanol, and 2.00 g of ion-exchanged 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. 12.1 g of 0.01 M hydrochloric acid and 2.6 mg of sodium chloride were added to the resulting mixture, 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 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. 12.1 g of a 0.01 M aqueous nitric acid solution and 3.7 mg of sodium nitrate were added to the resulting mixture, 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 bottle to prepare Binder Solution 7.

[0393] The compounds used in the examples and comparative examples are as follows: (Compound A) CF ３ O (CF ２ CF ２ O) １５ (CF ２ O) １６ CF ２ CH ２ OCH ２ CH ２ CH ２ Si[CH ２ CH ２ CH ２ Si(OCH ３ ) ３ ] ３ (Compound B) CF ３ CF2CF2O(CF ２ CF ２ CF ２O) ２０ CF ２ CF ２ CONHCH ２ C[CH ２ CH ２ CH ２ Si(OCH ３ ) ３ ] ３ (Compound C) CF ３ O (CF ２ CF ２ OCF ２ CF ２ CF ２ CF ２ O) １３ CF ２ CF ２ OCF ２ CF ２ CF ２ C(O)NHCH ２ C[CH ２ CH ２ CH ２ Si(OCH ３ ) ３ ] ３

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

[0395] (Example 1) <Formation of binder layer> Chemically strengthened glass (manufactured by Corning Incorporated, Gorilla Glass, thickness 0.7 mm) was irradiated with UV / O for 10 minutes. ３ After dry cleaning by treatment, the substrate was treated by spin coating at 3000 rpm for 30 seconds with binder solution 1. Thereafter, heat treatment was carried out in an oven at 150° C. for 2 hours to obtain binder layer 1.

[0396] <Formation of Surface Treatment Layer> The chemically strengthened glass with the binder layer obtained above was subjected to UV / O irradiation for 10 minutes. ３ After dry cleaning by treatment, the substrate was treated with surface treatment agent A by spin coating at 3000 rpm for 30 seconds, followed by heat treatment in an oven at 150°C for 30 minutes to obtain a surface treatment layer.

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

[0398] Comparative Examples 3 to 5 Silicon oxide (SiO 2 manufactured by Canon Optron) was deposited on a molybdenum boat in a vacuum deposition apparatus. ２ The above-mentioned chemically strengthened glass was placed in a vacuum deposition apparatus, and silicon oxide was vacuum-deposited on the ion-cleaned surface to obtain a binder layer 8.

[0399] The surface treatment agents 1 to 3 were applied to the obtained binder layer 8 in the same manner as in Example 1 to obtain a surface treatment layer with a binder layer.

[0400] (Surface Analysis TOF-SIMS, Analysis of Alkali Metals) The average sodium concentration in a region of the silicon oxide layer at a depth of 0.1 nm or more and 0.3 nm or less from the surface in contact with the water- and oil-repellent layer was determined using a time-of-flight secondary ion mass spectrometry (TOF-SIMS) device according to the following procedure.

[0401] (I) First, a standard sample for quantifying sodium concentration was prepared. A quartz glass substrate with the same composition as the silicon oxide layer to be evaluated was prepared, and sodium ions were implanted into this substrate to prepare a standard sample. A medium current ion implanter (IMX-3500RS manufactured by ULVAC, Inc.) was used for the ion implantation, with an energy of 110 keV and a sodium implantation dose of 6.0 × 10 １４ ions / cm ２ It was decided.

[0402] (II) Next, the substrate with silicon oxide to be evaluated and the standard sample prepared in (I) are simultaneously transported into the TOF-SIMS device, and TOF-SIMS depth direction analysis is performed by ion sputtering in order. The sputtering time (seconds, horizontal axis) and ２３ Na ＋ and ２８ Si ＋ A profile of the intensity (counts, vertical axis) of the sample was obtained.

[0403] Next, from the profile of the substrate prepared in (I), the sputtering rate (nm / sec) of the sputter ions and the coefficient for converting the count number into the amount of sodium per unit volume (atoms / (counts cm ３ The analysis conditions for the TOF-SIMS used here 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: 100 us Number of pixels: 128 x 128 pixels Sputter ion species: C ６０ ＋＋ Sputtering acceleration voltage: 10 keV Sputtering current value: 1 nA (at 10 kHz) Sputtering ion raster size: 1000 x 1000 μm ２ Sputtering time per time: 2 seconds Vacuum degree: 5.0 x 10 －６ mbar (no oxygen flow into the device) Neutralization gun: None

[0404] (III) Finally, from the depth profile of the sodium concentration of the silicon oxide obtained in (II), the average value of the sodium concentration in the region of the silicon oxide layer from a depth of 0.1 nm to 0.3 nm from the surface in contact with the water- and oil-repellent layer was calculated. The number of plotted points in the depth direction of the sodium concentration in the region of 0.1 nm to 0.3 nm was three. The average value of the sodium concentration was calculated as the average value of these three points. When the measurement was performed under the above conditions, three plotted points may be present in the region from a depth of 0.1 nm to 0.3 nm from the surface in contact with the oil-repellent layer.

[0405] In this example, the substrate with silicon oxide was subjected to 10 minutes of UV / O before TOF-SIMS depth profile analysis by ion sputtering. ３ The average sodium concentration in the silicon oxide layer in a region having a depth of 0.1 nm or more and 0.3 nm or less from the surface in contact with the water- and oil-repellent layer was calculated, and the results are shown in Table 1.

[0406] It is desirable that the silicon oxide layer be exposed before TOF-SIMS depth profile analysis by ion sputtering. That is, if a water-repellent / oil-repellent layer exists on the surface of the silicon oxide layer or if surface contamination is clearly progressing, it is preferable to remove these. Removal methods include oxygen plasma treatment, UV / O ３ It may be better to carry out both of these treatments depending on the thickness of the water- and oil-repellent layer and the degree of surface contamination.

[0407] (Surface Analysis TOF-SIMS Analysis) In the silicon oxide layer, Cl in the region of 0.1 nm to 0.3 nm deep from the surface in contact with the water-repellent and oil-repellent layer was － , S.O. ３ － , NO ３ － , S.O. ４ ２－ , P.O. ３ － and P.O. ４ 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 oxide substrate to be evaluated and the standard sample for quantifying the sodium concentration described above are simultaneously transported into the TOF-SIMS device, and a TOF-SIMS depth profile analysis is performed by ion sputtering in order. The sputtering time (seconds, horizontal axis) and the Cl concentration are measured. － , S.O. ３ － , NO ３ － , S.O. ４ ２－ , P.O. ３ － and P.O. ４ ３－ , SiO ２ － and Si － A profile of the intensity (counts, vertical axis) of the sputtered ions was then obtained. The sputtering rate (nm / sec) of the sputtered ions was then calculated from the profile of the standard sample substrate. The TOF-SIMS analysis conditions used here 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: 100 us Number of pixels: 128 x 128 pixels Sputter ion species: C ６０ ＋＋ Sputtering acceleration voltage: 10 keV Sputtering current value: 1 nA (at 10 kHz) Sputtering ion raster size: 300 x 300 μm ２ Sputtering time per cycle: 4 seconds Vacuum degree: 5.0 x 10 －６ mbar (no oxygen flow into the device) Neutralization gun: None

[0409] (II) Next, from the depth profile of the silicon oxide obtained in (I), the Cl content in the silicon oxide layer in the region of 0.1 nm to 0.3 nm deep from the surface in contact with the water- and oil-repellent layer was determined. － , S.O. ３ － , NO ３ － , S.O. ４ ２－ , P.O. ３ － and P.O. ４ ３－ , SiO ２ － and Si － The average counts of each of the above and the average counts of the six types were calculated. The number of points plotted in the region of 0.1 nm or more and 0.3 nm or less was three. － , S.O. ３ － , NO ３ － , S.O. ４ ２－ , P.O. ３ － , P.O. ４ ３－ , SiO ２ － and Si －When the measurement is performed under the above conditions, three plots may be present in the region of a depth of 0.1 nm or more and 0.3 nm or less from the surface in contact with the oil-repellent layer.

[0410] In the silicon oxide layer, in a region having a depth of 0.1 nm or more and 0.3 nm or less from the surface in contact with the water-repellent and oil-repellent layer, － , S.O. ３ － , NO ３ － , S.O. ４ ２－ , P.O. ３ － , P.O. ４ ３－ , SiO ２ － or Si － ) / (total ion count) fraction was calculated, and if it was 1.0% or more, it was determined that Cl － , S.O. ３ － , NO ３ － , S.O. ４ ２－ , P.O. ３ － , P.O. ４ ３－ , SiO ２ － or Si － For example, the silicon oxide layer used in Example 1 was found to have a high concentration of (NO ３ － ) / (total ion count) is 3.7%, and NO ３ － In the silicon oxide layer, Cl was detected in the region of 0.1 nm to 0.3 nm deep from the surface in contact with the water-repellent and oil-repellent layer. － , S.O. ３ － , NO ３ － , S.O. ４ ２－ , P.O. ３ － , P.O. ４ ３－ , SiO ２ － or Si －The detection results are shown in Table 1.

[0411]

[0412] (Abrasion Resistance Evaluation) <Initial Evaluation> For the initial evaluation (0 abrasion times), after the formation of the surface treatment layer, the excess water on the surface was wiped off, and then the static contact angle of water was measured. The contact angle was measured using a fully automatic contact angle meter DropMaster 700 (manufactured by Kyowa Interface Science Co., Ltd.) in an environment of 25°C. Specifically, the substrate having the surface treatment layer to be measured was placed horizontally, water was dropped onto the surface from a microsyringe, and a still image was taken with a video microscope 1 second after the drop to measure the static contact angle. The static contact angle was measured at five different points on the surface treatment layer of the substrate, and if the average value calculated was 100° or more, it was marked as ◯, and if it was less than 100°, it was marked as ×.

[0413] <Evaluation after abrasion resistance test> The following friction element was brought into contact with the formed surface treatment layer, a load of 5 N was applied thereto, and the friction element was moved back and forth at a speed of 40 mm / sec while the load was applied. When the number of frictions reached 10,000, the static contact angle of water was measured, and a value of 0 if it was 100° or more was evaluated as ◯, and a value of x 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 used as a friction element. Composition of artificial sweat: Anhydrous disodium hydrogen phosphate: 2 g Sodium chloride: 20 g 85% lactic acid: 2 g Histidine hydrochloride: 5 g Distilled water: 1 kg Silicone rubber processed product: A silicone rubber stopper SR-51 manufactured by Tigers Polymer was processed into a cylindrical shape with a diameter of 1 cm and a thickness of 1 cm.

[0415]

Claims

1. A substrate (A), a water- and oil-repellent layer (C), and a water- and oil-repellent layer (C) disposed between the substrate (A) and the water- and oil-repellent layer (C), the water- and oil-repellent layer (C) containing an alkali metal atom and Cl. － , NO ３ － , S.O. ３ － , S.O. ４ ２－ , P.O. ３ － and P.O. ４ ３－ and a silicon oxide layer (B) containing one or more selected from the group consisting of: wherein the silicon oxide layer (B) has an average alkali metal atom concentration of 1.4 × 10 in a region having a depth of 0.1 to 0.3 nm from the surface in contact with the water- and oil-repellent layer (C). １８ atoms / cm ３ Above 2.0 x 10 １９ atoms / cm ３ 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, and the silane compound has a fluorine atom.

2. The article of claim 1, wherein said alkali metal atoms comprise sodium atoms.

3. The silicon oxide layer (B) is － , S.O. ３ － and NO ３ － The article according to claim 1 or 2, comprising one or more selected from the group consisting of:

4. The silicon oxide layer (B) is composed of sodium atoms and Cl － , S.O. ３ － and NO ３ － The article according to any one of claims 1 to 3, comprising one or more selected from the group consisting of:

5. The article according to any one of claims 1 to 4, wherein the silicon oxide layer (B) comprises one or more materials selected from the group consisting of condensates of silicic acid compounds and hydrolysates of alkoxysilanes.

6. The article according to any one of claims 1 to 5, wherein the silicon oxide layer (B) is formed from a binder composition, and the binder composition contains a silicon oxide precursor, an acid, and an alkali metal salt.

7. The article according to any one of claims 1 to 6, wherein the silicon oxide layer (B) is formed from a liquid binder composition, and the liquid binder composition contains a silicon oxide precursor, an acid, an alkali metal salt, and a solvent.

8. The article according to claim 6 or 7, wherein the silicon oxide precursor comprises one or more compounds selected from the group consisting of silicic acid compounds, condensates of silicic acid compounds, alkoxysilanes, and hydrolysis condensates of alkoxysilanes.

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

10. The silane compound is represented by the formula (1) or (2), where R Ｓｉ is represented by the following formula (S1), (S2), (S3), (S4) or (S5): [In the formula: R １１ are each independently a hydroxyl group or a hydrolyzable group, R １２ are each independently a monovalent organic group, and n1 is (SiR １１ ｎ１ R １２ ３－ｎ１ ) units are each independently an integer of 0 to 3, １１ are each independently a single bond or a divalent organic group, １３ are each independently a hydrogen atom or a monovalent organic group, each t is independently an integer of 2 or more, R １４ are each independently a hydrogen atom, a halogen atom or -X １１ -SiR １１ ｎ１ R １２ ３－ｎ１ and R １５ are each independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms; R ａ１ are each independently -Z １ -SiR ２１ ｐ１ R ２２ ｑ１ R ２３ ｒ１ and Z １ are each independently a divalent organic group, ２１ are each independently -Z １’ -SiR ２１’ ｐ１’ R ２２’ ｑ１’ R ２３’ ｒ１’ and R ２２ are each independently a hydroxyl group or a hydrolyzable group, R ２３ are each independently a monovalent organic group, p1 is each independently an integer of 0 to 3, q1 is each independently an integer of 0 to 3, r1 is each independently an integer of 0 to 3, Z １’ are each independently a divalent organic group, ２１’ are each independently -Z １” -SiR ２２” ｑ１” R ２３” ｒ１” and R ２２’ are each independently a hydroxyl group or a hydrolyzable group, R ２３’ are each independently a monovalent organic group, p1' are each independently an integer of 0 to 3, q1' are each independently an integer of 0 to 3, r1' are each independently an integer of 0 to 3, Z １” are each independently a divalent organic group, ２２” are each independently a hydroxyl group or a hydrolyzable group, R ２３” are each independently a monovalent organic group; q1" are each independently an integer of 0 to 3; r1" are each independently an integer of 0 to 3; R ｂ１ are each independently a hydroxyl group or a hydrolyzable group, R ｃ１ are each independently a monovalent organic group, k1 is each independently an integer of 0 to 3, l1 is each independently an integer of 0 to 3, and m1 is each independently an integer of 0 to 3, provided that in formula (S3), there are at least two Si atoms bonded to a hydroxyl group or a hydrolyzable group, and R ｄ１ are each independently -Z ２ -CR ３１ ｐ２ R ３２ ｑ２ R ３３ ｒ２ and Z ２ are each independently a single bond, an oxygen atom, or a divalent organic group, and R ３１ are each independently -Z ２’ -CR ３２’ ｑ２’ R ３３’ ｒ２’ and R ３２ are each independently -Z ３ -SiR ３４ ｎ２ R ３５ ３－ｎ２ and R ３３ are each independently a hydrogen atom, a hydroxyl group, or a monovalent organic group; p2 is each independently an integer of 0 to 3; q2 is each independently an integer of 0 to 3; r2 is each independently an integer of 0 to 3; Z ２’ are each independently a single bond, an oxygen atom, or a divalent organic group, and R ３２’ are each independently -Z ３ -SiR ３４ ｎ２ R ３５ ３－ｎ２ and R ３３’ are each independently a hydrogen atom, a hydroxyl group, or a monovalent organic group; q2' are each independently an integer of 0 to 3; r2' are each independently an integer of 0 to 3; Z ３ are each independently a single bond, an oxygen atom, or a divalent organic group; R ３４ are each independently a hydroxyl group or a hydrolyzable group, R ３５ are each independently a monovalent organic group, n2 is each independently an integer of 0 to 3, R ｅ１ are each independently -Z ３ -SiR ３４ ｎ２ R ３５ ３－ｎ２ and R ｆ１ are each independently a hydrogen atom, a hydroxyl group, or a monovalent organic group, k2 is each independently an integer of 0 to 3, l2 is each independently an integer of 0 to 3, and m2 is each independently an integer of 0 to 3. However, in formula (S4), there are at least two Si atoms bonded to a hydroxyl group or a hydrolyzable group, and R ｇ１ and R ｈ１ are each 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 R ｆ１ ｍ２ and Z ４ are each independently a single bond, an oxygen atom, or a divalent organic group, with the proviso that in formula (S5), there are at least two Si atoms bonded to hydroxyl groups or hydrolyzable groups.

11. A method for manufacturing an article, comprising: a substrate (A); a water- and oil-repellent layer (C) formed from a silane compound containing Si atoms to which hydroxyl groups or hydrolyzable groups are bonded; and a water- and oil-repellent layer (C) disposed between the substrate (A) and the water- and oil-repellent layer (C) and containing alkali metal atoms and Cl. － , NO ３ － , S.O. ３ － , S.O. ４ ２－ , P.O. ３ － and P.O. ４ ３－ and a silicon oxide layer (B) containing one or more selected from the group consisting of: wherein the silicon oxide layer (B) has an average alkali metal atom concentration of 1.4 × 10 in a region having a depth of 0.1 to 0.3 nm from the surface in contact with the water- and oil-repellent layer (C). １８ atoms / cm ３ Above 2.0 x 10 １９ atoms / cm ３ and the silane compound has a fluorine atom.

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