Vapor deposition material, method for producing substrate with base layer, method for producing substrate with water-repellent and oil-repellent layer

Abstract

Provided is a vapor deposition material capable of forming a base layer capable of uniformly forming a water-repellent and oil-repellent layer, wherein the water-repellent and oil-repellent layer is formed by a condensate of a fluorine-containing compound having a reactive silyl group. A vapor deposition material comprising an oxide, wherein the oxide comprises: silicon; and at least one element I selected from the group consisting of elements of Group 1, Group 2, Group 13, Group 15, and transition metal elements of the periodic table, wherein the moisture content of the vapor deposition material is less than 2.0% by mass.

Description

Technical Field

[0001] The present invention relates to a vapor deposition material, a method for producing a substrate with a base layer, and a method for producing a substrate with a water- and oil-repellent layer. Background Art

[0002] In order to impart water- and oil-repellency, fingerprint-removability, lubricity (smoothness when touched with a finger), etc. to the surface of a substrate, it is known that a water- and oil-repellent layer formed of a condensate of the fluorinated compound is formed on the surface of the substrate by surface treatment with a fluorinated compound having a reactive silyl group.

[0003] In addition, in order to improve the adhesion between substrate and the water- and oil-repellent layer, sometimes a base layer is set between them. The

[0204] section of patent documentation 1 and the

[0076] section of patent documentation 2 record that a base layer formed by silicon oxide is set between substrate and the water- and oil-repellent layer. These base layers are formed by vapor deposition.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2014-218639

[0007] Patent Document 2: Japanese Patent Application Publication No. 2012-72272 Summary of the invention

[0008] Problem that the invention aims to solve

[0009] On the other hand, according to the difference of the type of the evaporation material for forming the base layer, if it is desired to form a water-repellent and oil-repellent layer formed by the condensation product of the fluorine-containing compound with reactive silyl group on the base layer, the water-repellent and oil-repellent layer will not be formed evenly on the base layer sometimes. The inventor finds: when the evaporation material is placed in a high temperature and humid environment, this problem is easily generated. It should be noted that the water-repellent and oil-repellent layer will not be formed evenly and refers to: the situation of the defective area that does not form the water-repellent and oil-repellent layer is produced on the base layer, the situation of observing foreign matter in the water-repellent and oil-repellent layer, the situation of observing foreign matter in the base layer, etc.

[0010] Therefore, an object of the present invention is to provide a vapor deposition material capable of forming an undercoat layer capable of uniformly forming a water- and oil-repellent layer formed of a condensate of a fluorine-containing compound having a reactive silyl group.

[0011] Another object of the present invention is to provide a method for producing a substrate with a base layer and a method for producing a substrate with a water- and oil-repellent layer.

[0012] Solutions for solving problems

[0013] The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by the following configuration.

[0014] [1] A vapor deposition material comprising an oxide, wherein the oxide comprises: silicon; and at least one element selected from the group consisting of Group 1 elements, Group 2 elements, Group 13 elements, Group 15 elements, and transition metal elements in the periodic table, wherein the moisture content of the vapor deposition material is less than 2.0% by mass.

[0015] [2] The vapor deposition material according to [1], wherein the water content is 50 mass ppm or more.

[0016] [3] The vapor deposition material according to [1] or [2], which is a sintered body or a molten body.

[0017] [4] A method for producing a substrate with a base layer, wherein a base layer including an oxide including the silicon and the element is formed on the substrate by vapor deposition using the vapor deposition material described in any one of [1] to [3] above.

[0018] [5] A method for producing a substrate with a water- and oil-repellent layer, wherein a base layer comprising an oxide is formed on the substrate by vapor deposition using the vapor deposition material described in any one of [1] to [3], wherein the oxide comprises the silicon and the element.

[0019] Next, a water- and oil-repellent layer is formed on the base layer. The water- and oil-repellent layer is formed from a condensate of a fluorine-containing compound having a reactive silyl group.

[0020] [6] The method for producing a substrate with a water- and oil-repellent layer according to [5], wherein the fluorine-containing compound is applied onto the base layer and condensed by a dry coating method or a wet coating method.

[0021] [7] The method for producing a substrate with a water- and oil-repellent layer according to [5] or [6], wherein the reactive silyl group is a group represented by the following formula (2).

[0022] -Si(R) n L 3-n ···(2)

[0023] Here, R is a monovalent hydrocarbon group, L is a hydrolyzable group or a hydroxyl group, and n is an integer of 0 to 2.

[0024] [8] The method for producing a substrate with a water- and oil-repellent layer according to any one of [5] to [7], wherein the fluorine-containing compound is a fluorine-containing compound having two or more reactive silyl groups.

[0025] [9] The method for producing a substrate with a water- and oil-repellent layer according to any one of [5] to [8], wherein the fluorine-containing compound is a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a reactive silyl group.

[0026]

[10] The method for producing a substrate with a water- and oil-repellent layer according to [9], wherein the poly(oxyfluoroalkylene) chain is a poly(oxyfluoroalkylene) chain mainly composed of an oxyperfluoroalkylene group.

[0027] Effects of the Invention

[0028] According to the present invention, there is provided a vapor deposition material capable of forming an underlayer on which a water- and oil-repellent layer composed of a condensate of a fluorine-containing compound having a reactive silyl group can be uniformly formed.

[0029] Furthermore, according to the present invention, a method for producing a substrate with a base layer and a method for producing a substrate with a water- and oil-repellent layer can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a cross-sectional view showing an example of a base material with a base layer obtained by the method of the present invention.

[0031] Figure 2 This is a cross-sectional view showing an example of a substrate with a water- and oil-repellent layer obtained by the method of the present invention. DETAILED DESCRIPTION

[0032] The meanings of the terms in the present invention are as follows.

[0033] In this specification, the unit represented by formula (1) is referred to as "unit (1)". The units represented by other formulae are described similarly. The group represented by formula (2) is referred to as "group (2)". The groups represented by other formulae are described similarly. The compound represented by formula (3) is referred to as "compound (3)". The compounds represented by other formulae are described similarly.

[0034] In the present specification, when "the alkylene group may have an A group", the alkylene group may have an A group between carbon atoms in the alkylene group, or may have an A group at a terminal such as alkylene-A group-.

[0035] The meanings of the terms in the present invention are as follows.

[0036] The "divalent organopolysiloxane residue" refers to a group represented by the following formula. x It is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group. In addition, g1 is an integer of 1 or more, preferably an integer of 1 to 9, and particularly preferably an integer of 1 to 4.

[0037]

[0038] The "silylphenylene backbone group" is -Si(R y )2PhSi(R y )2-(wherein Ph is phenylene, R y is a monovalent organic group). y , preferably an alkyl group (preferably having 1 to 10 carbon atoms).

[0039] "Dialkylsilylene" is -Si(R z )2-(where R z It is a group represented by an alkyl group (preferably having 1 to 10 carbon atoms).

[0040] The "number average molecular weight" of a compound is determined by using 1 H-NMR and 19 F-NMR was calculated by determining the number (average value) of oxyfluoroalkylene groups based on the terminal groups.

[0041] The content of each element in the evaporation material, unless otherwise specified, is the value measured by wet analysis. The content of each element provided by wet analysis is the mass percentage concentration (mass %). Atomic absorption is used for the determination of elements in Group 1 of the periodic table, and inductively coupled plasma (ICP) emission spectrometry or ICP mass spectrometry is used for the determination of other elements, and quantification is performed by the standard curve (matrix matching) method. It should be noted that the ratio of the molar concentrations of each element can be calculated based on the mass % of each element obtained by wet analysis and the atomic weight (g / mol) of each element.

[0042] For ease of explanation, Figure 1-2 The size ratio in the diagram is different from the actual size ratio.

[0043] [Evaporation materials]

[0044] The evaporation material of the present invention comprises an oxide, wherein the oxide comprises: silicon; and at least one element selected from the group consisting of elements of Group 1, elements of Group 2, elements of Group 13, elements of Group 15 and transition metal elements of the periodic table (hereinafter referred to as "element I"), and the water content of the evaporation material is less than 2.0% by mass.

[0045] In the present invention, the vapor deposition material refers to a material used for vapor deposition. The vapor deposition material of the present invention can be suitably used to form a base layer in a substrate with a water- and oil-repellent layer described later.

[0046] The inventors of the present invention etc. think: as the reason that the water-repellent and oil-repellent layer cannot be formed uniformly on the base layer in the prior art, it is that the formation state of the base layer intervenes.More specifically, it can be considered: when the base layer is formed by the evaporation of the evaporation material, the fragments of the evaporation material are given to the substrate in the form of agglomerates to form a part of the base layer, and it is difficult to form the water-repellent and oil-repellent layer in this region.Or, even if the water-repellent and oil-repellent layer is formed, the agglomerates are also easily removed due to post-treatment, and therefore, the water-repellent and oil-repellent layer also disappears in a lump.And then it is considered: as the reason for producing the fragments of this evaporation material during evaporation, it is that the water content in the evaporation material intervenes, and the desired effect can be obtained by reducing its content.

[0047] The water content of the vapor deposition material is less than 2.0 mass %, preferably 1.5 mass % or less, particularly preferably 1.0 mass % or less, from the viewpoint of being able to more uniformly form a water-repellent and oil-repellent layer (hereinafter also referred to as "water-repellent and oil-repellent layer") formed by a condensate of a fluorine-containing compound having a reactive silyl group.

[0048] The lower limit of the water content of the vapor deposition material is 10 mass ppm or more. From the viewpoint of better adhesion of the water- and oil-repellent layer to the base layer, it is preferably 50 mass ppm or more, more preferably 100 mass ppm or more, and particularly preferably 200 mass ppm or more.

[0049] The method for measuring the water content of the vapor deposition material is as follows.

[0050] The vapor deposition material was placed in an environment at 300°C, and the amount of water vapor produced was quantified using the Karl Fischer method (coulometric titration).

[0051] Examples of methods for adjusting the moisture content of the vapor deposition material include a method of adjusting heating conditions (eg, heating temperature) in the method for producing the vapor deposition material described below and a method of leaving the vapor deposition material to stand in an environment of predetermined temperature and humidity.

[0052] The first group elements of the periodic table (hereinafter also referred to as "first group elements") refer to lithium, sodium, potassium, rubidium and cesium. From the viewpoint of being able to form a water-repellent and oil-repellent layer more uniformly on the base layer, lithium, sodium and potassium are preferred, and sodium and potassium are particularly preferred. The first group elements may include only one or more.

[0053] The second group element of the periodic table (hereinafter also referred to as "the second group element") refers to beryllium, magnesium, calcium, strontium and barium, and is preferably magnesium, calcium, and barium, and is particularly preferably magnesium and calcium, from the viewpoint of being able to form a water-repellent and oil-repellent layer more uniformly on the base layer. The second group element may include only one or more.

[0054] The 13th group element of the periodic table (hereinafter also referred to as "the 13th group element") refers to boron, aluminum, gallium and indium. From the viewpoint of being able to form a water-repellent and oil-repellent layer more uniformly on the base layer, boron, aluminum and gallium are preferred, and boron and aluminum are particularly preferred. The 13th group element may include only one or more.

[0055] The 15th group element of the periodic table (hereinafter also referred to as "the 15th group element") refers to nitrogen, phosphorus, arsenic, antimony and bismuth. From the viewpoint of being able to form a water-repellent and oil-repellent layer more uniformly on the base layer, phosphorus, antimony and bismuth are preferably used, and phosphorus and bismuth are particularly preferably used. The 15th group element may include only one or more.

[0056] Transition metal elements refer to elements existing between Group 3 elements to Group 11 elements in the periodic table.

[0057] The oxide contained in the vapor deposition material can be a mixture of oxides of the above-mentioned elements (silicon, element I) alone (for example, a mixture of silicon oxide and the oxide of element I), or a composite oxide containing two or more of the above-mentioned elements, or a mixture of oxides of the above-mentioned elements alone and composite oxides.

[0058] From the viewpoint of achieving better abrasion resistance of the water- and oil-repellent layer, the content of oxides in the deposition material is preferably 80 mass % or more, more preferably 95 mass % or more, and particularly preferably 100 mass % (the deposition material is entirely oxides) relative to the total mass of the deposition material.

[0059] From the viewpoint of the better wear resistance of the water-repellent and oil-repellent layer, the oxygen content in the evaporation material is measured by the molar concentration (mol %) of oxygen in the evaporation material relative to all elements, preferably 40 to 70 mol %, more preferably 50 to 70 mol %, and particularly preferably 60 to 70 mol %. The oxygen content in the evaporation material is measured by XPS analysis of a substance obtained by fully crushing and pelletizing the evaporation material.

[0060] The vapor deposition material is composed of particles containing the above-mentioned oxide.

[0061] From the viewpoint of being able to form a water-repellent and oil-repellent layer more uniformly on the base layer, in the vapor deposition material, the mass ratio of particles having a particle size of 0.5 to 22.4 mm relative to the total mass of all particles is preferably 90% by mass or more, particularly preferably 95% by mass or more. The upper limit can be 100% by mass.

[0062] It should be noted that the particle size of the above particles corresponds to the size of each particle and refers to the major diameter.

[0063] The mass ratio of the above particles is measured by the following method.

[0064] All particles were sieved using a test sieve of JIS Z8801-1 standard - a metal mesh sieve with a nominal opening of 500 μm (0.5 mm) and 22.4 mm, and the mass of each particle size distribution was measured to calculate the ratio of the mass of each particle size to the total mass.

[0065] In the volume-based particle size distribution of particles constituting the vapor deposition material, the particle size when the cumulative number of particles is 10% is defined as D10, and the particle size when the cumulative number of particles is 90% is defined as D90, and the ratio of D90 to D10 (D90 / D10) is preferably 6.0 or less, and particularly preferably 5.0 or less. There is a view that if the above ratio is within the above range, the composition deviation between particles when making particles will be reduced.

[0066] The above ratio is preferably 2.0 or more.

[0067] The particle size distribution is measured by the following method.

[0068] All particles were sieved using a test sieve according to JIS Z8801-1 standard - a metal mesh sieve with a nominal mesh size of 300 μm, 500 μm, 1.0 mm, 4.75 mm, 9.5 mm, and 22.4 mm. The mass of each particle size distribution was measured, and a particle size distribution curve was prepared to calculate D90 / D10.

[0069] Examples of methods for adjusting the particle size and particle size distribution include a method of adjusting production conditions when producing the vapor deposition material and a method of applying a sieve having a predetermined mesh size.

[0070] From the viewpoint of better abrasion resistance of the water- and oil-repellent layer, the silicon content in the vapor-deposited material is preferably 10 to 99.8 mol %, more preferably 15 to 99.8 mol %, and particularly preferably 20 to 99.7 mol %, calculated as the molar concentration (mol %) of silicon in the vapor-deposited material relative to all elements except oxygen.

[0071] From the viewpoint of better abrasion resistance of the water- and oil-repellent layer, the silicon content in the vapor-deposited material, measured as the mass percentage concentration (mass %) of silicon in the vapor-deposited material relative to all elements except oxygen, is preferably 10 to 99.9 mass %, more preferably 20 to 99.9 mass %, and particularly preferably 30 to 99.8 mass %.

[0072] From the viewpoint of further improving the wear resistance of the water- and oil-repellent layer, the ratio of the total molar concentration of element I in the vapor deposition material to the molar concentration of silicon is preferably 0.003 to 9.0, more preferably 0.003 to 2.0, and particularly preferably 0.003 to 0.5.

[0073] When the total content of the element I in the evaporation material is expressed by the mass % of oxide benchmark, it is preferably more than 0.5 mass %, particularly preferably more than 1 mass % relative to the evaporation material total mass. If the content of element I is the above range, it is possible to stably form a base layer on the surface of the substrate by evaporation, and it is difficult to produce the shortcomings caused by the scattering of the evaporation material in the base layer. As a result, the adhesion of the base layer and the water-repellent and oil-repellent layer is excellent, and the wear resistance of the water-repellent and oil-repellent layer is excellent, so it is preferred. The upper limit can list 95 mass %.

[0074] From the viewpoint of better abrasion resistance of the water- and oil-repellent layer, the total content of element I in the vapor deposition material is calculated as the total mass percentage concentration (mass %) of element I in the vapor deposition material relative to all elements except oxygen, and is preferably 0.001 to 90 mass %, more preferably 0.001 to 80 mass %, and particularly preferably 0.001 to 70 mass %.

[0075] When the content of the element I in the vapor deposition material is within the above range, Si—O—Si bonds are sufficiently formed in the base layer, the mechanical properties of the base layer are sufficiently ensured, and the water- and oil-repellent layer has excellent abrasion resistance, which is preferred.

[0076] The vapor deposition material may contain one or more of the above elements as element I. When two or more elements are contained, the total content of the two or more elements satisfies the above range.

[0077] Specific examples of the form of the vapor deposition material include powder, melt, sintered body, granulated body, and crushed body. From the viewpoint of easy adjustment of the water content, sintered body and molten body are preferred.

[0078] Here, a sintered body refers to a solid obtained by sintering a powder of a vapor deposition material. If necessary, a molded body can be used instead of the powder of the vapor deposition material by pressurizing the powder. A molten body refers to a solid obtained by melting the powder of the vapor deposition material at a high temperature and then cooling and solidifying it. A granulated body refers to a solid obtained by mixing the powder of the vapor deposition material with a liquid medium (such as water, an organic solvent) to obtain particles, and then drying the particles.

[0079] The vapor deposition material can be produced by, for example, the following method.

[0080] A method of mixing a powder of silicon oxide and a powder of an oxide of element I to obtain a powder of a vapor deposition material.

[0081] A method of obtaining granules of the vapor deposition material by kneading the above-mentioned vapor deposition material powder and water to obtain particles, and then drying the particles.

[0082] In order to improve the yield during granulation and to make the element distribution in the granules uniform, the diameter of the raw silicon oxide powder is preferably 0.1 μm to 100 μm. When silicon oxide powders of 100 μm or more are used as raw materials, they are preferably crushed before use. In order to improve the strength of the granules, or to avoid sticking during firing when obtaining sintered bodies, the drying temperature is preferably above 60°C. On the other hand, in order to completely remove moisture, it is preferred to dry under reduced pressure (absolute pressure is 50 kPa or less).

[0083] A method of mixing a powder containing silicon (e.g., a powder composed of silicon oxide, silica sand, or silica disilicide gel), a powder of element I (e.g., a powder of an oxide of element I), and water, drying the resulting mixture, and then calcining the dried mixture, a compact obtained by pressure-molding the mixture, or the aforementioned granulated body to obtain a sintered body.

[0084] In order to reduce the hygroscopicity of the sintered body after sintering, the sintering temperature is preferably 900°C or higher, more preferably 1000°C or higher. In order to prevent damage to the transport container (packaging bag) when transporting the sintered body and to prevent contamination from the container, particles without protrusions are preferred, and spherical particles are more preferred. In order to remove the protrusions, it is preferred to add a protrusion removal process.

[0085] A method of obtaining a melt by melting a powder containing silicon (e.g., powder of silicon oxide, silica sand, or silica gel) and a powder of element I (e.g., powder of an oxide of element I) at high temperature and then cooling and solidifying the melt.

[0086] The production conditions in the above method are appropriately adjusted so that the water content in the vapor deposition material falls within the above range.

[0087] For example, in the method of obtaining a sintered body, the sintering temperature is preferably 300° C. or higher, particularly preferably 500° C. or higher. The upper limit of the sintering temperature is 2000° C. or lower.

[0088] [Method for producing a substrate with a base layer]

[0089] The method for producing a substrate with an underlayer of the present invention is a method for forming an underlayer including an oxide including silicon and element I on a substrate by a vapor deposition method using the vapor deposition material of the present invention.

[0090] A specific example of the vapor deposition method using a vapor deposition material is a vacuum vapor deposition method. The vacuum vapor deposition method is a method in which a vapor deposition material is evaporated in a vacuum chamber and attached to the surface of a substrate.

[0091] The temperature during vapor deposition (for example, the temperature of a boat on which the vapor deposition material is placed when a vacuum vapor deposition apparatus is used) is preferably 100 to 3000°C, particularly preferably 500 to 3000°C.

[0092] The pressure during vapor deposition (for example, the pressure in a tank where the vapor deposition material is placed when a vacuum vapor deposition apparatus is used) is preferably 1 Pa or less, particularly preferably 0.1 Pa or less.

[0093] When the base layer is formed using a vapor deposition material, one vapor deposition material may be used, or two or more vapor deposition materials containing different elements may be used.

[0094] Specific examples of the evaporation method of the evaporation material include: a resistance heating method in which the evaporation material is melted and evaporated on a resistance heating boat made of a high melting point metal; and an electron gun method in which an electron beam is irradiated on the evaporation material to directly heat the evaporation material to melt the surface and evaporate it. As the evaporation method of the evaporation material, the electron gun method is preferred from the viewpoint that the high melting point material can also be evaporated due to the ability to heat locally, and from the viewpoint that there is no need to worry about reaction with the container or impurities being mixed in because the part not in contact with the electron beam is at a low temperature.

[0095] In order to prevent contamination of regions or parts where deposition is not desired (for example, the back surface of the substrate) during deposition, there is a method of covering the regions or parts where deposition is not desired with a protective film.

[0096] After vapor deposition, it is preferred to perform additional humidification treatment from the viewpoint of improving film quality. The temperature during the humidification treatment is preferably 25 to 160° C., the relative humidity is preferably 40% or more, and the treatment time is preferably 1 hour or more.

[0097] Figure 1 1 is a cross-sectional view schematically showing an example of a base material with a base layer produced by the method of the present invention. The base material with a base layer 10 includes a base material 12 and a base layer 14 formed on one surface of the base material 12 .

[0098] exist Figure 1 In the example shown in FIG. 1 , the substrate 12 is in contact with the base layer 14 , but the invention is not limited thereto. The substrate with a base layer may have another layer (not shown) between the substrate 12 and the base layer 14 .

[0099] exist Figure 1 In the example shown in FIG. 1 , the base layer 14 is formed on the entire surface of the substrate 12 . However, the present invention is not limited thereto, and the base layer 14 may be formed only on a partial region of the substrate 12 .

[0100] exist Figure 1 In the example, the base layer 14 is formed only on one surface of the substrate 12 , but the present invention is not limited thereto, and the base layer 14 may be formed on both surfaces of the substrate 12 .

[0101] (Base material)

[0102] As substrate, owing to being able to impart water and oil repellency, therefore, it is particularly preferred that the substrate requiring imparting water and oil repellency is imparted. As the specific example of the material of substrate, metal, resin, glass, sapphire, ceramic, stone and their composite materials can be listed. Glass can be chemically strengthened.

[0103] As the substrate, a substrate for a touch panel or a substrate for a display is preferred, and a substrate for a touch panel is particularly preferred. The substrate for a touch panel preferably has light transmittance. "Having light transmittance" means that the vertical incidence visible light transmittance based on JIS R3106:1998 (ISO 9050:1990) is 25% or more. As the material for the substrate for a touch panel, glass and transparent resin are preferred.

[0104] In addition, the following examples can be cited as substrates: Glass products or resin products used in building materials, decorative building materials, decorative items, transportation equipment (such as automobiles), billboards / bulletin boards, water dispensers / tableware, sinks, ornamental utensils (such as frames, boxes), experimental equipment, furniture, art / sports / games. Glass products or resin products used in the outer packaging parts (except the display part) of mobile phones (such as smart phones), portable information terminals, game consoles, remote controllers, etc.

[0105] The substrate may be in the form of a plate or a film.

[0106] Base material can be a surface or two sides implemented the base material of surface treatment such as corona discharge treatment, plasma treatment, plasma graft polymerization.Implemented in the surface treated, the adhesion of base material and base layer is more excellent, and as a result, the wear resistance of water-repellent and oil-repellent layer is more excellent.Therefore, preferably the surface of the side contacting with the base layer of base material is implemented surface treatment.

[0107] (basal layer)

[0108] The base layer includes an oxide including at least silicon and element I.

[0109] The oxide contained in the base layer may contain only one of the above-mentioned elements as the element I, or may contain two or more of them.

[0110] The oxide contained in the base layer can be a mixture of oxides of the above-mentioned elements (silicon and element I) (for example, a mixture of silicon oxide and oxide of element I), or a composite oxide containing the above-mentioned elements, or a mixture of oxides of the above-mentioned elements and composite oxides.

[0111] The base layer may be a layer in which the components contained are uniformly distributed (hereinafter also referred to as a "homogeneous layer"), or a layer in which the components contained are non-uniformly distributed (hereinafter also referred to as an "inhomogeneous layer"). Specific examples of inhomogeneous layers include a case where a concentration gradient of a component (horizontally or vertically in the plane formed by the layer) is generated in the layer (gradient structure), and a case where other components are discontinuously present in a continuously present component (island structure).

[0112] The base layer may be a single layer or a multi-layer layer, but is preferably a single layer from the viewpoint of providing a more excellent abrasion resistance of the water- and oil-repellent layer.

[0113] The thickness of the base layer is preferably 1 to 100 nm, more preferably 1 to 50 nm, and particularly preferably 2 to 20 nm. If the thickness of the base layer is above the above lower limit, the adhesion of the water-repellent and oil-repellent layer based on the base layer is further improved, and the wear resistance of the water-repellent and oil-repellent layer is more excellent. If the thickness of the base layer is below the above upper limit, the wear resistance of the base layer itself is excellent.

[0114] The thickness of the base layer is measured by observing a cross section of the base layer using a transmission electron microscope (TEM).

[0115] [Method for producing a substrate having a water- and oil-repellent layer]

[0116] The method for manufacturing a substrate with a water-repellent and oil-repellent layer of the present invention is as described in the method for manufacturing a substrate with a base layer of the present invention, and the following method can be listed: a base layer comprising an oxide is formed on a substrate by a vapor deposition method using the vapor deposition material of the present invention, wherein the oxide comprises silicon and element I, and then a water-repellent and oil-repellent layer formed by a condensate of a fluorine-containing compound having a reactive silyl group is formed on the base layer.

[0117] The water- and oil-repellent layer can also be formed by using a composition containing a fluorine-containing compound or a fluorine-containing compound and a liquid medium (hereinafter also referred to as a "composition") by any production method of dry coating or wet coating.

[0118] Specific examples of the liquid medium included in the composition include water and organic solvents. Specific examples of the organic solvent include fluorine-based organic solvents and non-fluorine-based organic solvents. The organic solvent may be used alone or in combination of two or more.

[0119] Specific examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluorinated alkyl ethers, fluorinated alkyl amines, and fluorinated alcohols.

[0120] The fluorinated alkane is preferably a compound having 4 to 8 carbon atoms, and examples thereof include C6F 13 H (AC-2000: product name, made by AGC), C6F13 C2H5 (AC-6000: product name, manufactured by AGC Corporation), C2F5CHFCHFCF3 (Vertrel: product name, manufactured by DuPont Corporation).

[0121] Specific examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, 1,3-bis(trifluoromethyl)benzene, and 1,4-bis(trifluoromethyl)benzene.

[0122] The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms, and examples thereof include CF3CH2OCF2CF2H (AE-3000: product name, manufactured by AGC), C4F9OCH3 (Novec-7100: product name, manufactured by 3M), C4F9OC2H5 (Novec-7200: product name, manufactured by 3M), and C2F5CF(OCH3)C3F7 (Novec-7300: product name, manufactured by 3M).

[0123] Specific examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.

[0124] Specific examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

[0125] As non-fluorine-based organic solvents, preferred are compounds consisting only of hydrogen atoms and carbon atoms; and compounds consisting only of hydrogen atoms, carbon atoms and oxygen atoms, specifically, hydrocarbon-based organic solvents, ketone-based organic solvents, ether-based organic solvents, ester-based organic solvents, and alcohol-based organic solvents.

[0126] Specific examples of the hydrocarbon-based organic solvent include hexane, heptane, and cyclohexane.

[0127] Specific examples of the ketone organic solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.

[0128] Specific examples of the ether-based organic solvent include diethyl ether, tetrahydrofuran, and tetraethylene glycol dimethyl ether.

[0129] Specific examples of the ester organic solvent include ethyl acetate and butyl acetate.

[0130] Specific examples of the alcohol-based organic solvent include isopropyl alcohol, ethanol, and n-butanol.

[0131] The content of the fluorine-containing compound in the composition is preferably from 0.01 to 50.00% by mass, particularly preferably from 1.0 to 30.00% by mass, based on the total mass of the composition.

[0132] The content of the liquid medium in the composition is preferably 50.00 to 99.99% by mass, particularly preferably 70.00 to 99.00% by mass, based on the total mass of the composition.

[0133] The water- and oil-repellent layer can be produced, for example, by the following method.

[0134] A method of forming a water- and oil-repellent layer on the surface of the base layer by treating the surface of the base layer by a dry coating method using a fluorine-containing compound.

[0135] A method of forming a water- and oil-repellent layer on the surface of a base layer by applying the composition on the surface of the base layer by a wet coating method and drying the composition.

[0136] As a specific example of the dry coating method, vacuum evaporation method, CVD method, sputtering method can be listed. Among these, from the viewpoint of suppressing the decomposition of fluorinated compounds and the viewpoint of device simplicity, vacuum evaporation method is preferably used. During vacuum evaporation, a granular material obtained by loading a metal porous body such as iron or steel with a fluorinated compound or impregnating a composition and drying can be used.

[0137] Specific examples of the wet coating method include spin coating, wipe coating, spray coating, blade coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Blodgett method, and gravure coating.

[0138] In order to improve the wear resistance of the water-repellent and oil-repellent layer, as required, the operation for promoting the reaction of the fluorinated compound with reactive silyl group and the base layer can be carried out. As this operation, heating, humidification, light irradiation etc. can be listed. For example, in the atmosphere with moisture, the base material with the base layer of the water-repellent and oil-repellent layer is heated, and the hydrolysis reaction of the reactive silyl group hydrolyzing into silanol group can be promoted, and the condensation reaction of the silanol group of the silanol group generating siloxane bond, the base layer surface silanol group and the fluorinated compound silanol group is reacted by the condensation reaction of the silanol group.

[0139] After surface treatment, the compound that is in the water-repellent and oil-repellent layer and does not chemically bond with other compounds, silicon oxide layer can be removed as required. As a specific method, for example, the method that the water-repellent and oil-repellent layer flows with solvent, the method that the cloth that is impregnated with solvent is wiped, the method that the water-repellent and oil-repellent layer surface is acid-cleaned etc. can be listed.

[0140] Figure 2 The cross-sectional view schematically shows an example of a substrate with a water-repellent and oil-repellent layer manufactured by the method of the present invention. The substrate 20 with a water-repellent and oil-repellent layer has a substrate 22, a base layer 24 formed on one surface of the substrate 22, and a water-repellent and oil-repellent layer 26 formed on the surface of the base layer 24.

[0141] In addition, Figure 2 In the example, the water- and oil-repellent layer 26 is formed on the entire surface of the base layer 24 , but the invention is not limited thereto, and the water- and oil-repellent layer 26 may be formed only on a partial region of the base layer 24 .

[0142] exist Figure 2 In the example, the base layer 24 and the water- and oil-repellent layer 26 are formed only on one surface of the substrate 22 , but the present invention is not limited thereto, and the base layer 24 and the water- and oil-repellent layer 26 may be formed on both surfaces of the substrate 22 .

[0143] (Water and oil repellent layer)

[0144] The water- and oil-repellent layer is formed of a condensate of a fluorine-containing compound having a reactive silyl group.

[0145] The reactive silyl group refers to a hydrolyzable silyl group and a silanol group (Si—OH). Specific examples of the hydrolyzable silyl group include a group in which L of the group represented by the formula 2 described below is a hydrolyzable group.

[0146] The hydrolyzable silyl group forms the silanol group shown in Si-OH by hydrolysis reaction.Silanol group further undergoes dehydration condensation reaction between silanol groups to form Si-O-Si key.In addition, silanol group can undergo dehydration condensation reaction with the silanol group derived from oxide contained in the base layer to form Si-O-Si key.That is, when at least a portion of the reactive silyl group is a hydrolyzable silyl group, the water-repellent and oil-repellent layer comprises the condensation product obtained by hydrolysis reaction and dehydration condensation reaction of the reactive silyl group of fluorinated compound.When the reactive silyl group is all silanol groups, the water-repellent and oil-repellent layer comprises the condensation product obtained by dehydration condensation reaction of the silanol group of fluorinated compound.As the reactive silyl group possessed by fluorinated compound, it is preferred that at least a portion thereof is a hydrolyzable silyl group.

[0147] The thickness of the water-repellent and oil-repellent layer is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. If the thickness of the water-repellent and oil-repellent layer is above the lower limit, the effect of the water-repellent and oil-repellent layer can be fully obtained. If the thickness of the water-repellent and oil-repellent layer is below the upper limit, the utilization efficiency is high.

[0148] The thickness of the water- and oil-repellent layer can be calculated from the vibration period of an interference pattern of reflected X-rays obtained by X-ray reflectivity (XRR) using an X-ray diffractometer for thin film analysis.

[0149] <Fluorine-containing compound having a reactive silyl group>

[0150] The fluorine-containing compound having a reactive silyl group is preferably a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a reactive silyl group, from the viewpoint of excellent water- and oil-repellency of the water- and oil-repellent layer.

[0151] The poly(oxyfluoroalkylene) chain comprises a plurality of units represented by formula (1).

[0152] (OX)···(1)

[0153] X is a fluoroalkylene group having one or more fluorine atoms.

[0154] The fluoroalkylene group preferably has 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms, from the viewpoint of achieving better weather resistance and corrosion resistance of the water- and oil-repellent layer.

[0155] The fluoroalkylene group may be linear or branched, but is preferably linear from the viewpoint of achieving more excellent effects of the present invention.

[0156] The number of fluorine atoms in the fluoroalkylene group is preferably 1 to 2 times, particularly preferably 1.7 to 2 times, the number of carbon atoms, from the viewpoint of providing a more excellent corrosion resistance of the water- and oil-repellent layer.

[0157] The fluoroalkylene group may be a group in which all hydrogen atoms in the fluoroalkylene group are substituted with fluorine atoms (perfluoroalkylene group).

[0158] Specific examples of the unit (1) include -OCHF-, -OCF2CHF-, -OCHFCF2-, -OCF2CH2-, -OCH2CF2-, -OCF2CF2CHF-, -OCHFCF2CF2-, -OCF2CF2CH2-, -OCH2CF2CF2-, -OCF2CF2CF2CH2-, -OCH2CF2CF2CF2-, -OCF2CF2CF2CF2CH2-, -OCH2CF 2CF2CF2CF2-, -OCF2CF2CF2CF2CF2CH2-, -OCH2CF2CF2CF2CF2CF2-, -OCF2-, -OCF2CF2-, -OCF2CF2CF2-, - OCF(CF3)CF2-, -OCF2CF2CF2CF2-, -OCF(CF3)CF2CF2-, -OCF2CF2CF2CF2CF2-, -OCF2CF2CF2CF2CF2CF2-.

[0159] The number m of repetitions of the unit (1) contained in the poly(oxyfluoroalkylene) chain is 2 or more, more preferably an integer of 2-200, further preferably an integer of 5-150, particularly preferably an integer of 5-100, and most preferably an integer of 10-50.

[0160] The poly(oxyfluoroalkylene) chain may contain two or more units (1). Examples of the two or more units (1) include two or more units (1) having different numbers of carbon atoms; two or more units (1) having the same number of carbon atoms but different in the presence or absence of side chains or in the types of side chains; and two or more units (1) having the same number of carbon atoms but different in the number of fluorine atoms.

[0161] The bonding order of two or more types of (OX) is not limited, and they may be arranged randomly, alternately, or in blocks.

[0162] In order to obtain a film having excellent fingerprint stain removability, the poly(oxyfluoroalkylene) chain is preferably a poly(oxyfluoroalkylene) chain mainly composed of units (1) belonging to oxyperfluoroalkylene. m In the poly(oxyfluoroalkylene) chain shown, the ratio of the number of units (1) belonging to oxyperfluoroalkylene to the total number m of units (1) is preferably 50 to 100%, more preferably 80 to 100%, particularly preferably 90 to 100%.

[0163] As the poly(oxyfluoroalkylene) chain, a poly(oxyperfluoroalkylene) chain and a poly(oxyperfluoroalkylene) chain having one or two oxyfluoroalkylene units having a hydrogen atom at one terminal or both terminals are more preferred.

[0164] As the (OX) of the poly(oxyfluoroalkylene) chain m , preferably (OCH ma F (2-ma) ) m11 (OC2H mb F (4-mb) ) m12 (OC3H mc F (6-mc) ) m13 (OC4H md F (8-md) ) m14 (OC5H me F (10-me) ) m15 (OC6H mf F (12-mf) ) m16 .

[0165] ma is 0 or 1, mb is an integer of 0-3, mc is an integer of 0-5, md is an integer of 0-7, me is an integer of 0-9, and mf is an integer of 0-11.

[0166] m11, m12, m13, m14, m15 and m16 are each independently an integer greater than or equal to 0, and preferably less than or equal to 100.

[0167] m11+m12+m13+m14+m15+m16 is an integer greater than or equal to 2, more preferably an integer from 2 to 200, more preferably an integer from 5 to 150, further preferably an integer from 5 to 100, and particularly preferably an integer from 10 to 50.

[0168] Among them, m12 is preferably an integer greater than 2, and particularly preferably an integer from 2 to 200.

[0169] In addition, C3H mc F (6-mc) 、C4H md F (8-md) 、C5H me F (10-me) and C6H mf F (12-mf) The polyol may be linear or branched, but is preferably linear from the viewpoint of providing a more excellent abrasion resistance of the water- and oil-repellent layer.

[0170] It should be noted that the above formula represents the type and number of units, not the arrangement of the units. That is, m11 to m16 represent the number of units. For example, (OCH ma F (2-ma) ) m11 Does not indicate m11 (OCH ma F (2-ma) ) units are continuous blocks. Similarly, (OCH ma F (2-ma) )~(OC6H mf F (12-mf) ) does not mean that they are arranged in that order.

[0171] In the above formula, when two or more of m11 to m16 are not 0 (i.e., (OX) m When the structure is composed of two or more types of units, the arrangement of the different units may be any of a random arrangement, an alternating arrangement, a block arrangement, and a combination of these arrangements.

[0172] Furthermore, for each of the above units, when two or more units are included, these units may be different. For example, when m11 is 2 or more, multiple (OCH ma F (2-ma) ) can be the same or different.

[0173] The reactive silyl group is preferably a group represented by formula (2).

[0174] -Si(R) n L 3-n ···(2)

[0175] The number of groups (2) possessed by the fluorinated ether compound is 1 or more, preferably 2 or more, more preferably 2 to 10, further preferably 2 to 5, particularly preferably 2 or 3, from the viewpoint of better abrasion resistance of the water- and oil-repellent layer.

[0176] When a plurality of groups (2) are present in one molecule, the plurality of groups (2) may be the same or different, and are preferably the same from the viewpoint of easy availability of raw materials and easy production of the fluorinated ether compound.

[0177] R is a monovalent hydrocarbon group, preferably a monovalent saturated hydrocarbon group. The number of carbon atoms in R is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2.

[0178] L is a hydrolyzable group or a hydroxyl group.

[0179] The hydrolyzable group is a group that forms a hydroxyl group by hydrolysis reaction. That is, the hydrolyzable silyl group shown in Si-L forms a silanol group shown in Si-OH by hydrolysis reaction. The silanol group further reacts between the silanol groups to form a Si-O-Si bond. In addition, the silanol group and the silanol group derived from the oxide contained in the base layer undergo a dehydration condensation reaction, thereby being able to form a Si-O-Si bond.

[0180] Specific examples of the hydrolyzable group include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanate group (-NCO). As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferred. As the aryloxy group, an aryloxy group having 3 to 10 carbon atoms is preferred. Among them, the aryl group of the aryloxy group includes a heteroaryl group. As the halogen atom, a chlorine atom is preferred. As the acyl group, an acyl group having 1 to 6 carbon atoms is preferred. As the acyloxy group, an acyloxy group having 1 to 6 carbon atoms is preferred.

[0181] As L, from the viewpoint of easier production of the fluorine-containing ether compound, an alkoxy group having 1 to 4 carbon atoms and a halogen atom are preferred. As L, from the viewpoint of less outgassing during coating and better storage stability of the fluorine-containing ether compound, an alkoxy group having 1 to 4 carbon atoms is preferred, when long-term storage stability of the fluorine-containing ether compound is required, an ethoxy group is particularly preferred, and when the reaction time after coating is set to a short time, a methoxy group is particularly preferred.

[0182] n is an integer from 0 to 2.

[0183] n is preferably 0 or 1, particularly preferably 0. The presence of a plurality of Ls makes the adhesion of the water- and oil-repellent layer stronger.

[0184] When n is 1 or less, a plurality of L present in one molecule may be the same or different. From the viewpoint of the ease of obtaining raw materials and the ease of manufacturing the fluorinated ether compound, they are preferably the same. When n is 2, a plurality of R present in one molecule may be the same or different. From the viewpoint of the ease of obtaining raw materials and the ease of manufacturing the fluorinated ether compound, they are preferably the same.

[0185] As the fluorine-containing ether compound, a compound represented by formula (3) is preferred from the viewpoint of providing the water- and oil-repellent layer with more excellent water- and oil-repellency and abrasion resistance.

[0186] [A-(OX) m -O-] j Z[-Si(R) n L 3-n ] g ···(3)

[0187] A is a perfluoroalkyl group or -Q[-Si(R) n L 3-n ] k .

[0188] The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, particularly preferably 1 to 3, from the viewpoint of providing a more excellent abrasion resistance of the water- and oil-repellent layer.

[0189] The perfluoroalkyl group may be linear or branched.

[0190] Where A is -Q[-Si(R) n L 3-n ] k , j is 1.

[0191] Examples of the perfluoroalkyl group include CF3-, CF3CF2-, CF3CF2CF2-, CF3CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2CF2-, and CF3CF(CF3)-.

[0192] The perfluoroalkyl group is preferably CF3-, CF3CF2-, or CF3CF2CF2- from the viewpoint of providing a more excellent water- and oil-repellent layer.

[0193] Q is a (k+1)-valent linking group. As described below, k is an integer of 1 to 10. Therefore, examples of Q include linking groups having 2 to 11 valencies.

[0194] Q may be any group as long as it does not impair the effects of the present invention, and examples thereof include an alkylene group optionally having an ethereal oxygen atom or a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, a silicon atom, a di- to octavalent organopolysiloxane residue, and groups (g2-1) to (g2-9) and groups (g3-1) to (g3-9).

[0195] R, L, n, X and m are as defined above.

[0196] Z is a (j+g)-valent linking group.

[0197] Z may be any group as long as it does not impair the effects of the present invention, and examples thereof include an alkylene group optionally having an etheric oxygen atom or a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, a silicon atom, a di- to octavalent organopolysiloxane residue, and groups (g2-1) to (g2-9) and groups (g3-1) to (g3-9).

[0198] j is an integer of 1 or more, preferably an integer of 1 to 5 from the viewpoint of further improving the water- and oil-repellent properties of the water- and oil-repellent layer, and particularly preferably 1 from the viewpoint of easy production of the compound (3).

[0199] g is an integer of 1 or more, and is preferably an integer of 2 to 4, more preferably 2 or 3, and particularly preferably 3, from the viewpoint of achieving better abrasion resistance of the water- and oil-repellent layer.

[0200] As compound (3), from the viewpoint of the initial water contact angle and friction resistance of the water-repellent and oil-repellent layer being more excellent, preferably compound (3-11), compound (3-21) and compound (3-31). Among these, the initial water contact angle of the water-repellent and oil-repellent layer of compound (3-11) and compound (3-21) is particularly excellent, and the friction resistance of the water-repellent and oil-repellent layer of compound (3-31) is particularly excellent.

[0201] R f1 -(OX) m -OY 11 [-Si(R) n L 3-n ] g1 ···(3-11)

[0202] [R f2 -(OX) m -O-] j2 Y 21 [-Si(R) n L 3-n ] g2 ···(3-21)

[0203] [L 3-n (R)n Si-] k3 Y 32 -(OX) m -OY 31 [-Si(R) n L 3-n ] g3 ···(3-31)

[0204] In formula (3-11), X, m, R, n and L have the same definitions as X, m, R, n and L in formula (3), respectively.

[0205] R f1 It is a perfluoroalkyl group, and preferred embodiments and specific examples of the perfluoroalkyl group are as described above.

[0206] Y 11 It is a (g1+1)-valent linking group, and its specific examples are the same as those for Z in formula (3).

[0207] g1 is an integer of 2 or more, and is preferably an integer of 2 to 15, more preferably an integer of 2 to 4, further preferably 2 or 3, and particularly preferably 3, from the viewpoint of better abrasion resistance of the water- and oil-repellent layer.

[0208] In formula (3-21), X, m, R, n and L have the same definitions as X, m, R, n and L in formula (3), respectively.

[0209] R f2 It is a perfluoroalkyl group, and preferred embodiments and specific examples of the perfluoroalkyl group are as described above.

[0210] j2 is an integer greater than or equal to 2, preferably an integer of 2-6, and more preferably an integer of 2-4.

[0211] Y 21 It is a (j2+g2)-valent linking group, and its specific example is the same as Z in formula (3).

[0212] g2 is an integer of 2 or more, and is preferably an integer of 2 to 15, more preferably 2 to 6, further preferably 2 to 4, and particularly preferably 4, from the viewpoint of further improving the abrasion resistance of the water- and oil-repellent layer.

[0213] In formula (3-31), X, m, R, n and L have the same definitions as X, m, R, n and L in formula (3), respectively.

[0214] k3 is an integer greater than or equal to 1, preferably an integer of 1 to 4, more preferably 2 or 3, and particularly preferably 3.

[0215] Y 32 It is a (k3+1)-valent linking group, and its specific examples are the same as Q in formula (3).

[0216] Y 31 It is a (g3+1)-valent linking group, and its specific examples are the same as those for Z in formula (3).

[0217] g3 is an integer greater than or equal to 1, preferably an integer of 1 to 4, more preferably 2 or 3, and particularly preferably 3.

[0218] Y in formula (3-11) 11 It can be a group (g2-1) (wherein d1+d3=1 (in other words, d1 or d3 is 0), g1=d2+d4, d2+d4≥2), a group (g2-2) (wherein e1=1, g1=e2, e2≥2), a group (g2-3) (wherein g1=2), a group (g2-4) (wherein h1=1, g1=h2, h2≥2), a group (g2-5) (wherein i1=1, g1=i2, i2≥2), a group (g2-7) (wherein g1=i3+1), a group (g2-8) (wherein g1=i4, i4≥2) or a group (g2-9) (wherein g1=i5, i5≥2).

[0219] Y in formula (3-21) 21 It can be a group (g2-1) (where j2=d1+d3, d1+d3≥2, g2=d2+d4, d2+d4≥2), a group (g2-2) (where j2=e1, e1=2, g2=e2, e2=2), a group (g2-4) (where j2=h1, h1≥2, g2=h2, h2≥2) or a group (g2-5) (where j2=i1, i1=2, g2=i2, i2=2).

[0220] In addition, Y in formula (3-31) 31 and Y 32 Each of them can independently be a group (g2-1) (wherein g3=d2+d4, k3=d2+d4), a group (g2-2) (wherein g3=e2, k3=e2), a group (g2-3) (wherein g3=2, k3=2), a group (g2-4) (wherein g3=h2, k3=h2), a group (g2-5) (wherein g3=i2, k3=i2), a group (g2-6) (wherein g3=1, k3=1), a group (g2-7) (wherein g3=i3+1, k3=i3+1), a group (g2-8) (wherein g3=i4, k3=i4) or a group (g2-9) (wherein g3=i5, k3=i5).

[0221]

[0222] (-A 1 -) e1 C(Re2 ) 4-e1-e2 (-Q 22 -) e2 ···(g2-2)

[0223] -A 1 -N(-Q 23 -)2···(g2-3)

[0224] (-A 1 -) h1 Z 1 (-Q 24 -) h2 ···(g2-4)

[0225] (-A 1 -) i1 Si(R e3 ) 4-i1-i2 (-Q 25 -) i2 ···(g2-5)

[0226] -A 1 -Q 26 -···(g2-6)

[0227] -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-i3 (-Q 25 -) i3 ···(g2-7)

[0228] -A 1 -[CH2C(R e4 )(-Q 27 -)] i4 -R e5 ···(g2-8)

[0229] -A 1 -Z a (-Q 28 -) i5 ···(g2-9)

[0230] Among them, in formula (g2-1) to formula (g2-9), A 1 Side connection to (OX) m , Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 and Q 28 The side is connected to [-Si(R) n L3-n ].

[0231] A 1 is a single bond, an alkylene group, or a -C(O)NR group between carbon atoms of an alkylene group having 2 or more carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O- or -SO2NR 6 -group, in each formula, A 1 When there are more than 2, more than 2 A 1 The hydrogen atoms of the alkylene groups may be substituted by fluorine atoms.

[0232] Q 22 Alkylene; -C(O)NR between carbon atoms of alkylene with 2 or more carbon atoms 6 -、-C(O)-、-NR 6 - or -O-; having -C(O)NR at the end of the alkylene group not connected to Si 6 -、-C(O)-、-NR 6 - or -O-; or a group having -C(O)NR between carbon atoms of an alkylene group having 2 or more carbon atoms 6 -、-C(O)-、-NR 6 - or -O- and having -C(O)NR at the end of the side not connected to Si 6 -、-C(O)-、-NR 6 - or -O-, in each formula, Q 22 When there are more than 2, more than 2 Q 22 Can be the same or different.

[0233] Q 23 An alkylene group, or an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms 6 -、-C(O)-、-NR 6 - or -O- group, 2 Q 23 Can be the same or different.

[0234] About Q 24 , in Q 24 Bonded Z 1 If the atom in is a carbon atom, it is Q 22 , in Q 24 Bonded Z 1 If the atom in is a nitrogen atom, it is Q 23 , various types, Q 24 When there are more than 2, more than 2 Q24 Can be the same or different.

[0235] Q 25 An alkylene group, or an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms 6 -、-C(O)-、-NR 6 - or -O-, in each formula, Q 25 When there are more than 2, more than 2 Q 25 Can be the same or different.

[0236] Q 26 An alkylene group, or an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms 6 -、-C(O)-、-NR 6 - or -O-.

[0237] R 6 It is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

[0238] Q 27 is a single bond or an alkylene group.

[0239] Q 28 It is an alkylene group, or a group having an ethereal oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms.

[0240] Z 1 is a group having a h1+h2 valent ring structure, the ring structure having 1 A carbon atom or nitrogen atom directly bonded to Q 24 Directly bonded carbon or nitrogen atoms.

[0241] R e1 is a hydrogen atom or an alkyl group, in each formula, R e1 When there are two or more, two or more R e1 Can be the same or different.

[0242] R e2 It is a hydrogen atom, a hydroxyl group, an alkyl group or an acyloxy group.

[0243] R e3 It is an alkyl group.

[0244] R e4 is a hydrogen atom or an alkyl group, and is preferably a hydrogen atom from the viewpoint of easy preparation of the compound. e4 When there are two or more, two or more R e4 Can be the same or different.

[0245] Re5 It is a hydrogen atom or a halogen atom, and is preferably a hydrogen atom from the viewpoint of easy production of the compound.

[0246] d1 is an integer of 0-3, preferably 1 or 2. d2 is an integer of 0-3, preferably 1 or 2. d1+d2 is an integer of 1-3.

[0247] d3 is an integer of 0-3, preferably 0 or 1. d4 is an integer of 0-3, preferably 2 or 3. d3+d4 is an integer of 1-3.

[0248] d1+d3 for Y 11 or Y 21 is an integer of 1 to 5, preferably 1 or 2. 11 , Y 31 and Y 32 For , it is 1.

[0249] d2+d4 for Y 11 or Y 21 is an integer of 2 to 5, preferably 4 or 5, for Y 31 and Y 32 It is an integer of 3 to 5, preferably 4 or 5.

[0250] e1+e2 is 3 or 4. e1 is for Y 11 is 1 for Y 21 is an integer of 2 to 3, for Y 31 and Y 32 For Y 11 or Y 21 2 or 3 for Y 31 and Y 32 For example, 2 or 3.

[0251] h1 for Y 11 is 1 for Y 21 is an integer greater than 2 (preferably 2), and for Y 31 and Y 32 For Y 11 or Y 21 is an integer greater than 2 (preferably 2 or 3), and for Y 31 and Y 32 It is an integer greater than 1 (preferably 2 or 3).

[0252] i1+i2 for Y 11 3 or 4 for Y 12 For Y 31 and Y 32 For Y 11 is 1 for Y21 For Y 31 and Y 32 i2 is 1 for Y 11 2 or 3 for Y 12 For Y 31 and Y 32 For example, 2 or 3.

[0253] i3 is 2 or 3.

[0254] i4 for Y 11 For Y 31 and Y 32 In general, it is 1 or more (preferably an integer of 1 to 10, particularly preferably an integer of 1 to 6).

[0255] i5 is 2 or more, and preferably an integer of 2-7.

[0256] From the viewpoint of easy production of compound (3-11), compound (3-21) and compound (3-31) and the viewpoint that the water-repellent and oil-repellent layer has better abrasion resistance, light resistance and chemical resistance, Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 , Q 28 The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. However, the lower limit of the number of carbon atoms in the alkylene group when having a specific bond between carbon atoms is 2.

[0257] As Z 1 The ring structure in the ring structure may be the above ring structure, and the preferred form is also the same. It should be noted that, since A 1 , Q 24 Directly bonded to Z 1 Therefore, there is no ring structure connected to, for example, an alkylene group, the alkylene group and A 1 , Q 24 Connection situation.

[0258] Z a is an organopolysiloxane residue having a valence of (i5+1), preferably the following group. a It is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group.

[0259]

[0260] From the viewpoint of easy production of compound (3-11), compound (3-21) and compound (3-31), R e1 , R e2 , R e3 or R e4 The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-6, further preferably 1-3, particularly preferably 1-2.

[0261] From the viewpoint of easy production of compound (3-11), compound (3-21) and compound (3-31), R e2 The number of carbon atoms in the alkyl portion of the acyloxy group is preferably 1-10, more preferably 1-6, further preferably 1-3, particularly preferably 1-2.

[0262] From the viewpoint of easy production of compound (3-11), compound (3-21) and compound (3-31) and the viewpoint of better abrasion resistance and fingerprint removability of the water- and oil-repellent layer, h1 is preferably 1 to 6, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.

[0263] From the viewpoint of easy production of compound (3-11), compound (3-21) and compound (3-31) and the viewpoint of better abrasion resistance and fingerprint removability of the water- and oil-repellent layer, h2 is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 or 3.

[0264] As Y 11 Other forms of include group (g3-1) (wherein d1+d3=1 (in other words, d1 or d3 is 0), g1=d2×r1+d4×r1), group (g3-2) (wherein e1=1, g1=e2×r1), group (g3-3) (wherein g1=2×r1), group (g3-4) (wherein h1=1, g1=h2×r1), group (g3-5) (wherein i1=1, g1=i2×r1), group (g3-6) (wherein g1=r1), group (g3-7) (wherein g1=r1×(i3+1)), group (g3-8) (wherein g1=r1×i4), and group (g3-9) (wherein g1=r1×i5).

[0265] As Y 21Other forms of include group (g3-1) (where j2 = d1+d3, d1+d3≥2, g2 = d2×r1+d4×r1), group (g3-2) (where j2 = e1, e1=2, g2 = e2×r1, e2=2), group (g3-4) (where j2 = h1, h1≥2, g2 = h2×r1), and group (g3-5) (where j2 = i1, i1 is 2 or 3, g2 = i2×r1, i1+i2 is 3 or 4).

[0266] As Y 31 and Y 32 Other forms of the group include the group (g3-1) (wherein g3 = d2 × r1 + d4 × r1, k3 = d2 × r1 + d4 × r1), the group (g3-2) (wherein g3 = e2 × r1, k3 = e2 × r1), the group (g3-3) (wherein g3 = 2 × r1, k3 = 2 × r1), the group (g3-4) (wherein g3 = h2 × r1, k3 = h2 × r1), the group (g3- 5) (wherein g3 = i2 × r1, k3 = i2 × r1), group (g3-6) (wherein g3 = r1, k3 = r1), group (g3-7) (wherein g3 = r1 × (i3+1), k3 = r1 × (i3+1)), group (g3-8) (wherein g3 = r1 × i4, k3 = r1 × i4), group (g3-9) (wherein g3 = r1 × i5, k3 = r1 × i5).

[0267]

[0268] (-A 1 -) e1 C(R e2 ) 4-e1-e2 (-Q 22 -G 1 ) e2 ···(g3-2)

[0269] -A 1 -N(-Q 23 -G 1 )2···(g3-3)

[0270] (-A 1 -) h1 Z 1 (-Q 24 -G 1 ) h2 ···(g3-4)

[0271] (-A 1 -) i1 Si(R e3 )4-i1-i2 (-Q 25 -G 1 ) i2 ···(g3-5)

[0272] -A 1 -Q 26 -G 1 ···(g3-6)

[0273] -A 1 -CH(-Q 22 -G 1 )-Si(R e3 ) 3-i3 (-Q 25 -G 1 ) i3 ···(g3-7)

[0274] -A 1 -[CH2C(R e4 )(-Q 27 -G 1 )] i4 -R e5 ···(g3-8)

[0275] -A 1 -Z a (-Q 28 -G 1 ) i5 ···(g3-9)

[0276] Among them, in formula (g3-1) to formula (g3-9), A 1 Side connection to (OX) m , G 1 The side is connected to [-Si(R) n L 3-n ].

[0277] G 1 is a group (g3), in each formula, G 1 When there are two or more G 1 Can be the same or different. Except G 1 The symbols other than these are the same as those in formula (g2-1) to formula (g2-9).

[0278] -Si(R 8 ) 3-r1 (-Q 3 -) r1 ···(g3)

[0279] Among them, in formula (g3), the Si side is connected to Q 22 , Q 23 , Q24 , Q 25 , Q 26 , Q 27 and Q 28 , Q 3 The side is connected to [-Si(R) n L 3-n ]. 8 Q is an alkyl group. 3 Alkylene; -C(O)NR between carbon atoms of alkylene with 2 or more carbon atoms 6 -、-C(O)-、-NR 6 - or -O-; or -(OSi(R 9 )2) p -O-, 2 or more Qs 3 They can be the same or different. r1 is 2 or 3. 6 R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. 9 is alkyl, phenyl or alkoxy, 2 R 9 They may be the same or different. p is an integer from 0 to 5. When p is 2 or more, two or more (OSi(R 9 )2)Can be the same or different.

[0280] From the viewpoint of easy production of compound (3-11), compound (3-21) and compound (3-31) and the viewpoint that the water-repellent and oil-repellent layer has better abrasion resistance, light resistance and chemical resistance, Q 3 The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. However, the lower limit of the number of carbon atoms in the alkylene group when having a specific bond between carbon atoms is 2.

[0281] From the viewpoint of easy production of compound (3-11), compound (3-21) and compound (3-31), R 8 The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-6, further preferably 1-3, particularly preferably 1-2.

[0282] From the viewpoint of easy production of compound (3-11), compound (3-21) and compound (3-31), R 9 The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-6, further preferably 1-3, particularly preferably 1-2.

[0283] From the viewpoint of excellent storage stability of compound (3-11), compound (3-21) and compound (3-31), R 9The number of carbon atoms in the alkoxy group is preferably 1-10, more preferably 1-6, further preferably 1-3, particularly preferably 1-2.

[0284] p is preferably 0 or 1.

[0285] As compound (3-11), compound (3-21) and compound (3-31), for example, compounds of the following formula can be cited. From the viewpoint of industrial ease of manufacture, ease of handling, and superior water and oil repellency, friction resistance, fingerprint stain removal, lubricity, chemical resistance, light resistance and chemical resistance of the water and oil repellent layer, and particularly superior light resistance, the compounds of the following formula are preferred. In the compound of the following formula, R f With R in the above formula (3-11) f1 -(OX) m -O- or R in formula (3-21) f2 -(OX) m -O-, and the preferred embodiment is also the same. In the compound of the following formula, Q f and -(OX) in formula (3-31) m The preferred aspects are the same as -O-.

[0286] As Y 11 Examples of the compound (3-11) that is the group (g2-1) include compounds of the following formula.

[0287]

[0288] As Y 11 Examples of the compound (3-11) that is the group (g2-2) include compounds of the following formula.

[0289]

[0290] As Y 21 Examples of the compound (3-21) that is the group (g2-2) include compounds of the following formula.

[0291]

[0292] As Y 11 Examples of the compound (3-11) that is the group (g2-3) include compounds of the following formula.

[0293]

[0294] As Y 11 Examples of the compound (3-11) that is a group (g2-4) include compounds of the following formula.

[0295]

[0296] As Y 11 Examples of the compound (3-11) that is the group (g2-5) include compounds of the following formula.

[0297]

[0298] As Y 11 Examples of the compound (3-11) that is the group (g2-7) include compounds of the following formula.

[0299]

[0300] As Y 11 Examples of the compound (3-11) that is the group (g3-1) include compounds of the following formula.

[0301]

[0302] As Y 11 Examples of the compound (3-11) that is the group (g3-2) include compounds of the following formula.

[0303]

[0304] As Y 11 Examples of the compound (3-11) that is a group (g3-3) include compounds of the following formula.

[0305]

[0306] As Y 11 Examples of the compound (3-11) that is a group (g3-4) include compounds of the following formula.

[0307]

[0308] As Y 11 Examples of the compound (3-11) that is the group (g3-5) include compounds of the following formula.

[0309]

[0310] As Y 11 Examples of the compound (3-11) that is the group (g3-6) include compounds of the following formula.

[0311]

[0312] As Y 11 Examples of the compound (3-11) that is a group (g3-7) include compounds of the following formula.

[0313]

[0314] As Y 21 Examples of the compound (3-21) that is the group (g2-1) include compounds of the following formula.

[0315]

[0316] As Y 31 and Y 32 Examples of the compound (3-31) that is the group (g2-1) include compounds of the following formula.

[0317]

[0318] As Y 31 and Y 32 Examples of the compound (3-31) that is the group (g2-2) include compounds of the following formula.

[0319]

[0320] As Y 31 and Y 32 Examples of the compound (3-31) that is the group (g2-3) include compounds of the following formula.

[0321]

[0322] As Y 31 and Y 32 Examples of the compound (3-31) that is the group (g2-4) include compounds of the following formula.

[0323]

[0324] As Y 31 and Y 32 Examples of the compound (3-31) that is the group (g2-5) include compounds of the following formula.

[0325]

[0326] As Y 31 and Y 32 Examples of the compound (3-31) that is the group (g2-6) include compounds of the following formula.

[0327]

[0328] As Y 31 and Y 32Examples of the compound (3-31) that is the group (g2-7) include compounds of the following formula.

[0329]

[0330] As Y 31 and Y 32 Examples of the compound (3-31) that is the group (g3-2) include compounds of the following formula.

[0331]

[0332] As the fluorine-containing ether compound, a compound represented by the formula (3X) is also preferred from the viewpoint of providing a film with better water and oil repellency and abrasion resistance.

[0333] [A-(OX) m ] j Z'[-Si(R) n L 3-n ] g ···(3X)

[0334] From the viewpoint of providing a more excellent water- and oil-repellent layer, the compound (3X) is preferably a compound represented by the formula (3-1).

[0335] A-(OX) m -Z 31 ···(3-1)

[0336] In the formula (3-1), the definitions of A, X and m are the same as those of the groups in the formula (3).

[0337] Z' is a (j+g)-valent linking group.

[0338] Z' can be any group as long as it does not impair the effect of the present invention. For example, it includes an alkylene group optionally having an ethereal oxygen atom or a divalent organic polysiloxane residue, an oxygen atom, a carbon atom, a nitrogen atom, a silicon atom, a di- to octa-valent organic polysiloxane residue, and a group obtained by removing Si(R)nL3-n from formula (3-1A), formula (3-1B), and formulas (3-1A-1) to (3-1A-6).

[0339] Z 31 It is group (3-1A) or group (3-1B).

[0340] -Q a -X 31 (-Q b -Si(R) n L 3-n ) h (-R 31 ) i···(3-1A)

[0341] -Q c -[CH2C(R 32 )(-Q d -Si(R) n L 3-n )] y -R 33 ···(3-1B)

[0342] Q a It is a single bond or a divalent linking group.

[0343] Examples of the divalent linking group include a divalent hydrocarbon group, a divalent heterocyclic group, -O-, -S-, -SO2-, -N(R d )-、-C(O)-、-Si(R a )2-, and groups obtained by combining two or more of them. Here, R a is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group. d It is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).

[0344] Examples of the divalent hydrocarbon group include a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, an alkenylene group, and an alkynylene group. The divalent saturated hydrocarbon group may be linear, branched, or cyclic, and examples thereof include an alkylene group. The divalent saturated hydrocarbon group preferably has 1 to 20 carbon atoms. In addition, the divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, and examples thereof include a phenylene group. As the alkenylene group, an alkenylene group having 2 to 20 carbon atoms is preferred, and as the alkynylene group, an alkynylene group having 2 to 20 carbon atoms is preferred.

[0345] Examples of the group obtained by combining two or more of these groups include -OC(O)-, -C(O)N(R d )-, an alkylene group having an ethereal oxygen atom, an alkylene group having -OC(O)-, an alkylene group-Si(R a )2-phenylene-Si(R a )2.

[0346] X 31 It is a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom or a di- to octa-valent organopolysiloxane residue.

[0347] The alkylene group may have -O-, a silylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group. The alkylene group may have a plurality of groups selected from the group consisting of -O-, a silylene skeleton group, a divalent organopolysiloxane residue and a dialkylsilylene group.

[0348] X 31 The alkylene group shown has preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms.

[0349] Examples of the divalent to octavalent organopolysiloxane residues include divalent organopolysiloxane residues and (w+1)-valent organopolysiloxane residues described below.

[0350] Q b It is a single bond or a divalent linking group.

[0351] The definition of the divalent linking group is the same as that of Q a The same definition as described in .

[0352] R 31 It is a hydroxyl group or an alkyl group.

[0353] The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 carbon atom.

[0354] X 31 When it is a single bond or an alkylene group, h is 1 and i is 0.

[0355] X 31 When it is a nitrogen atom, h is an integer of 1 to 2, i is an integer of 0 to 1, and h+i=2 is satisfied.

[0356] X 31 When is a carbon atom or a silicon atom, h is an integer from 1 to 3, i is an integer from 0 to 2, and h+i=3 is satisfied.

[0357] X 31 When it is a di- to octa-valent organopolysiloxane residue, h is an integer of 1 to 7, i is an integer of 0 to 6, and h+i=1 to 7 is satisfied.

[0358] (-Q b -Si(R) n L 3-n ) exists 2 or more, 2 or more (-Q b -Si(R) n L 3-n ) can be the same or different. 31 When there are two or more, two or more (-R 31 ) can be the same or different.

[0359] Q c It is a single bond or an alkylene group which may have an etheric oxygen atom, and is preferably a single bond from the viewpoint of easy production of the compound.

[0360] The alkylene group which may have an etheric oxygen atom preferably has 1 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms.

[0361] R 32 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and is preferably a hydrogen atom from the viewpoint of easy production of the compound.

[0362] The alkyl group is preferably a methyl group.

[0363] Q d is a single bond or an alkylene group. The number of carbon atoms in the alkylene group is preferably 1 to 10, particularly preferably 1 to 6. From the viewpoint of easy production of the compound, Q d Preferred is a single bond or -CH2-.

[0364] R 33 It is a hydrogen atom or a halogen atom, and is preferably a hydrogen atom from the viewpoint of easy production of the compound.

[0365] y is an integer of 1-10, preferably an integer of 1-6.

[0366] More than 2 [CH2C(R 32 )(-Q d -Si(R) n L 3-n )] can be the same or different.

[0367] The group (3-1A) is preferably the group (3-1A-1) to (3-1A-6).

[0368] -(X 32 ) s1 -Q b1 -SiR n L 3-n ···(3-1A-1)

[0369] -(X 33 ) s2 -Q a2 -N[-Q b2 -Si(R) n3 L 3-n ]2···(3-1A-2)

[0370] -Q a3 -G(R g )[-Q b3 -Si(R) n L 3-n ]2···(3-1A-3)

[0371] -[C(O)N(R d )] s4 -Q a4 -(O) t4 -C[-(O) u4 -Q b4 -Si(R)n L 3-n ]3···(3-1A-4)

[0372] -Q a5 -Si[-Q b5 -Si(R) n L 3-n ]3···(3-1A-5)

[0373] -[C(O)N(R d )] v -Q a6 -Z a’ [-Q b6 -Si(R) n L 3-n ] w ···(3-1A-6)

[0374] In addition, in formulae (3-1A-1) to (3-1A-6), R, L and n are as defined above.

[0375] X 32 -O- or -C(O)N(R d )-(where N is bonded to Q b1 ).

[0376] R d The definition of is as above.

[0377] s1 is 0 or 1.

[0378] Q b1 The alkylene group may have -O-, a silylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group. The alkylene group may have a plurality of groups selected from the group consisting of -O-, a silylene skeleton group, a divalent organopolysiloxane residue and a dialkylsilylene group.

[0379] When the alkylene group has -O-, a silylphenylene skeleton group, a divalent organopolysiloxane residue, or a dialkylsilylene group, it is preferred that these groups be present between carbon atoms.

[0380] Q b1 The alkylene group shown has preferably 1 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms.

[0381] As Q b1When s1 is 0, preferably -CH2OCH2CH2CH2-, -CH2OCH2CH2OCH2CH2CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2OCH2CH2CH2Si(CH3)2OSi(CH3)2CH2CH2-. In (X 32 ) s1 In the case of -O-, -CH2CH2CH2- and -CH2CH2OCH2CH2CH2- are preferred. 32 ) s1 -C(O)N(R d )-, preferably an alkylene group having 2 to 6 carbon atoms (wherein N in the formula is bonded to Q b1 ). If Q b1 When it is these groups, the compound can be easily produced.

[0382] Specific examples of the group (3-1A-1) include the following groups. In the following formula, * represents the same group as (OX) m Bonding location.

[0383]

[0384] X 33 is -O-, -NH- or -C(O)N(R d )-.

[0385] R d The definition of is as above.

[0386] Q a2 It is a single bond, an alkylene group, -C(O)-, or a group having an ethereal oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms, -C(O)-, -C(O)O-, -OC(O)-, or -NH-.

[0387] Q a2 The alkylene group shown has preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms.

[0388] Q a2 The group having an ethereal oxygen atom, -C(O)-, -C(O)O-, -OC(O)- or -NH- between carbon atoms in the alkylene group having 2 or more carbon atoms preferably has 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms.

[0389] As Q a2From the viewpoint of easy production of compounds, preferred are -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2OCH2CH2-, -CH2NHCH2CH2-, -CH2CH2OC(O)CH2CH2-, and -C(O)- (wherein the right side is bonded to N).

[0390] s2 is 0 or 1 (where Q a2 When it is a single bond, it is 0). From the viewpoint of easy production of the compound, it is preferably 0.

[0391] Q b2 It is an alkylene group, or a group having a divalent organopolysiloxane residue, an ethereal oxygen atom, or -NH- between carbon atoms of an alkylene group having 2 or more carbon atoms.

[0392] Q b2 The alkylene group shown has preferably 1 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms.

[0393] Q b2 The group having a divalent organopolysiloxane residue, an etheric oxygen atom or -NH- between carbon atoms of the alkylene group having 2 or more carbon atoms preferably has 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms.

[0394] As Q b2 From the viewpoint of easy production of the compound, -CH2CH2CH2- and -CH2CH2OCH2CH2CH2- (wherein the right side is bonded to Si) are preferred.

[0395] 2 [-Q b2 -Si(R) n L 3-n ] can be the same or different.

[0396] Specific examples of the group (3-1A-2) include the following groups. In the following formula, * represents the same group as (OX) m Bonding location.

[0397]

[0398] Q a3 It is a single bond or an alkylene group which may have an etheric oxygen atom, and is preferably a single bond from the viewpoint of easy production of the compound.

[0399] The alkylene group which may have an etheric oxygen atom preferably has 1 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms.

[0400] G is a carbon atom or a silicon atom.

[0401] R gR is hydroxyl or alkyl. g The alkyl group shown preferably has 1 to 4 carbon atoms.

[0402] As G(R g ), preferably C(OH) or Si(R ga )(where R ga The alkyl group preferably has 1 to 10 carbon atoms, and is particularly preferably a methyl group).

[0403] Q b3 It is an alkylene group, or a group having an ethereal oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms.

[0404] Q b3 The alkylene group shown has preferably 1 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms.

[0405] Q b3 The group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms of the alkylene group having 2 or more carbon atoms preferably has 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms.

[0406] As Q b3 From the viewpoint of easy production of the compound, -CH2CH2-, -CH2CH2CH2-, and -CH2CH2CH2CH2CH2CH2CH2CH2CH2- are preferred.

[0407] 2 [-Q b3 -Si(R) n L 3-n ] can be the same or different.

[0408] Specific examples of the group (3-1A-3) include the following groups. In the following formula, * represents the same group as (OX) m Bonding location.

[0409]

[0410] R in formula (3-1A-4) d The definition of is as above.

[0411] s4 is 0 or 1.

[0412] Q a4 It is a single bond or an alkylene group which may have an ethereal oxygen atom.

[0413] The alkylene group which may have an etheric oxygen atom preferably has 1 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms.

[0414] t4 is 0 or 1 (where Q a4 When it is a single bond, it is 0).

[0415] AS-Q a4 -(O) t4 -, from the viewpoint of easy manufacture of the compound, when s4 is 0, preferably a single bond, -CH2O-, -CH2OCH2-, -CH2OCH2CH2O-, -CH2OCH2CH2OCH2-, -CH2OCH2CH2CH2OCH2- (wherein the left side is bonded to (OX) m ), when s4 is 1, it is preferably a single bond, -CH2-, or -CH2CH2-.

[0416] Q b4 is an alkylene group, and the alkylene group may have -O-, -C(O)N(R d )-(R d is as defined above), a silylphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group.

[0417] It should be noted that when the alkylene group has an -O- or silylphenylene skeleton group, it is preferred that the -O- or silylphenylene skeleton group be located between carbon atoms. d )-, dialkylsilylene or divalent organopolysiloxane residue, preferably between carbon atoms or with (O) u4 The terminal of the bonding side has these groups.

[0418] Q b4 The alkylene group shown has preferably 1 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms.

[0419] u4 is 0 or 1.

[0420] As - (O) u4 -Q b4 -, from the viewpoint of easy production of compounds, preferred are -CH2CH2-, -CH2CH2CH2-, -CH2OCH2CH2CH2-, -CH2OCH2CH2CH2CH2CH2-, -OCH2CH2CH2-, -OSi(CH3)2CH2CH2CH2-, -OSi(CH3)2OSi(CH3)2CH2CH2CH2-, -CH2CH2CH2Si(CH3)2PhSi(CH3)2CH2CH2- (wherein the right side is bonded to Si).

[0421] 3 [-(O) u4 -Q b4 -Si(R) n L3-n ] can be the same or different.

[0422] Specific examples of the group (3-1A-4) include the following groups. In the following formula, * represents the same group as (OX) m Bonding location.

[0423]

[0424] Q a5 It is an alkylene group which may have an ethereal oxygen atom.

[0425] The alkylene group which may have an etheric oxygen atom preferably has 1 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms.

[0426] As Q a5 From the viewpoint of easy production of compounds, preferred are -CH2OCH2CH2CH2-, -CH2OCH2CH2OCH2CH2CH2-, -CH2CH2-, and -CH2CH2CH2- (wherein the right side is bonded to Si).

[0427] Q b5 It is an alkylene group, or a group having an ethereal oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms.

[0428] Q b5 The alkylene group shown has preferably 1 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms.

[0429] Q b5 The group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms of the alkylene group having 2 or more carbon atoms preferably has 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms.

[0430] As Q b5 From the viewpoint of easy manufacture of the compound, preferably -CH2CH2CH2-, -CH2CH2OCH2CH2CH2- (wherein the right side is bonded to Si (R) n L 3-n ).

[0431] 3 [-Q b5 -Si(R) n L 3-n ] can be the same or different.

[0432] Specific examples of the group (3-1A-5) include the following groups. In the following formula, * represents the same group as (OX) m Bonding location.

[0433]

[0434] R in formula (3-1A-6) d The definition of is as above.

[0435] v is 0 or 1.

[0436] Q a6 It is an alkylene group which may have an ethereal oxygen atom.

[0437] The alkylene group which may have an etheric oxygen atom preferably has 1 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms.

[0438] As Q a6 From the viewpoint of easy manufacture of the compound, preferably -CH2OCH2CH2CH2-, -CH2OCH2CH2OCH2CH2CH2-, -CH2CH2-, -CH2CH2-, -CH2CH2CH2- (wherein the right side is bonded to Z a’ ).

[0439] Z a’ It is a (w+1)-valent organopolysiloxane residue.

[0440] w is 2 or more, and preferably an integer of 2-7.

[0441] Examples of the (w+1)-valent organopolysiloxane residue include the same groups as those described above for the (i5+1)-valent organopolysiloxane residue.

[0442] Q b6 It is an alkylene group, or a group having an ethereal oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms.

[0443] Q b6 The alkylene group shown has preferably 1 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms.

[0444] Q b6 The group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms of the alkylene group having 2 or more carbon atoms preferably has 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms.

[0445] As Q b6 From the viewpoint of easy production of the compound, -CH2CH2- and -CH2CH2CH2- are preferred.

[0446] w[-Q b6 -Si(R) n3 L 3-n ] can be the same or different.

[0447] From the viewpoint of further improving the water- and oil-repellent properties of the water- and oil-repellent layer, the compound (3X) is preferably a compound represented by the formula (3-2).

[0448] [A-(OX) m1 -Q a -] j32 Z 32 [-Q b -Si(R) n L 3-n ] h32 ···(3-2)

[0449] In formula (3-2), A, X, m, Q a , Q b The definitions of R and L are the same as those of the groups in formula (3-1) and formula (3-1A).

[0450] Z 32 It is a hydrocarbon group with a valence of (j32+h32), or a hydrocarbon group with a valence of (j32+h32) and having 2 or more carbon atoms and one or more etheric oxygen atoms between carbon atoms of the hydrocarbon group.

[0451] As Z 32 , preferably a residue obtained by removing a hydroxyl group from a polyol having a primary hydroxyl group.

[0452] As Z 32 From the viewpoint of easy availability of raw materials, groups represented by formula (Z-1) to formula (Z-5) are preferred. 34 It is an alkyl group, preferably a methyl group or an ethyl group.

[0453]

[0454] j32 is an integer of 2 or more, and is preferably an integer of 2 to 5 from the viewpoint of providing a more excellent water- and oil-repellent layer.

[0455] h32 is an integer of 1 or more, and is preferably an integer of 2 to 4, and more preferably 2 or 3, from the viewpoint of achieving better abrasion resistance of the water- and oil-repellent layer.

[0456] Specific examples of the fluorine-containing ether compound include those described in the following documents.

[0457] Perfluoropolyether-modified aminosilane described in Japanese Patent Application Laid-Open No. 11-029585 and Japanese Patent Application Laid-Open No. 2000-327772,

[0458] Silicon-containing organic fluorine-containing polymers described in Japanese Patent No. 2874715,

[0459] The organosilicon compound described in Japanese Patent Application Laid-Open No. 2000-144097,

[0460] Fluorinated silicone described in Japanese Patent Publication No. 2002-506887,

[0461] The organosilicone compound described in Japanese Patent Publication No. 2008-534696,

[0462] Fluorinated modified hydrogen polymers described in Japanese Patent No. 4138936,

[0463] Compounds described in U.S. Patent Application Publication No. 2010 / 0129672, International Publication No. 2014 / 126064, and Japanese Patent Application Publication No. 2014-070163,

[0464] The organosilicon compounds described in International Publication Nos. 2011 / 060047 and 2011 / 059430,

[0465] The fluorinated organosilane compound described in International Publication No. 2012 / 064649,

[0466] A polymer containing a fluorinated oxyalkylene group as described in Japanese Unexamined Patent Publication No. 2012-72272,

[0467] International Publication No. 2013 / 042732, International Publication No. 2013 / 121984, International Publication No. 2013 / 121985, International Publication No. 2013 / 121986, International Publication No. 2014 / 163004, Japanese Patent Application Publication No. 2014-080473, International Publication No. 2015 / 087902, International Publication No. 2017 / 038830, International Publication No. 2017 / 038832, International Publication No. 2017 / 187775, International Publication No. 2018 / 216630, International Publication No. 2019 / 039186, International Publication No. 2019 / 039226, International Publication No. 2019 / 039341, International Publication No. 2019 / 044479, International Publication No. 2019 / 049753, International Publication No. 2019 / 163282 and fluorine-containing ether compounds described in Japanese Patent Application Publication No. 2019-044158,

[0468] Silane compounds containing perfluoro(poly)ethers described in Japanese Patent Application Publication No. 2014-218639, International Publication No. 2017 / 022437, International Publication No. 2018 / 079743, and International Publication No. 2018 / 143433,

[0469] A perfluoro(poly)ether group-containing silane compound described in International Publication No. 2018 / 169002,

[0470] A fluorinated (poly)ether group-containing silane compound described in International Publication No. 2019 / 151442,

[0471] A (poly)ether group-containing silane compound described in International Publication No. 2019 / 151445,

[0472] A perfluoropolyether group-containing compound described in International Publication No. 2019 / 098230,

[0473] Fluoropolyether group-containing polymer-modified silanes described in Japanese Patent Application Laid-Open Nos. 2015-199906, 2016-204656, 2016-210854, and 2016-222859.

[0474] Commercially available products of fluorinated ether compounds include KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., Afluid (registered trademark) S550 manufactured by AGC Corporation, Optool (registered trademark) DSX, Optool (registered trademark) AES, Optool (registered trademark) UF503, Optool (registered trademark) UD509, etc. manufactured by Daikin Industries, Ltd.

[0475] Example

[0476] Hereinafter, the present invention will be described in detail by way of Examples, but the present invention is not limited to these Examples.

[0477] Examples 1 to 12 are embodiments, and Examples 13 to 15 are comparative examples.

[0478] [evaluate]

[0479] (Coating uniformity)

[0480] Under the condition of LED light irradiation, 100 glass substrates with a water-repellent and oil-repellent layer of 10 cm×10 cm were visually inspected. Among the substrates inspected, the case where the ratio of substrates without any defects in the total number of substrates was more than 90% was recorded as "○", and the case where the ratio of substrates without any defects in the total number of substrates was less than 90% was recorded as "×".

[0481] It should be noted that the defects refer to defective areas where the water- and oil-repellent layer is not formed on the base layer, foreign matter observed in the water- and oil-repellent layer, and foreign matter observed in the base layer.

[0482] (Abrasion resistance)

[0483] For the water-repellent and oil-repellent layer, according to JIS L0849:2013 (ISO 105-X12:2001), a reciprocating traverse tester (manufactured by KNT) was used to make steel wool BONSTAR (count: #0000, size: 5mm×10mm×10mm) reciprocate at a load of 9.8N and a speed of 80rpm. After 4,000 reciprocating steel wool abrasions, the water contact angle of the water-repellent and oil-repellent layer was measured, and the wear resistance was evaluated according to the following evaluation criteria. The smaller the reduction in the contact angle of water after abrasion, the smaller the performance reduction caused by abrasion, and the better the wear resistance.

[0484] ○: Water contact angle is 100 degrees or more

[0485] ×: The contact angle of water is less than 100 degrees

[0486] [Synthesis of fluorine-containing compounds]

[0487] Compound (3A) was obtained by referring to the method for producing compound (ii-2) described in International Publication No. 2014 / 126064.

[0488] CF3CF2-OCF2CF2-(OCF2CF2CF2CF2OCF2CF2) n -OCF2CF2CF2-C(O)NH-CH2CH2CH2-Si(OCH3)3···(3A)

[0489] The average value of the number of units n is 13. The number average molecular weight of compound (3A) is 4,920.

[0490] (Example 1)

[0491] Add 17.36 g of soda ash (Soda Ash Japan) and 243.66 g of silica particles SC5500-SQ (trade name, ADMATECS) to the Eirich high-powered stirrer EL-1 (manufactured by Eirich, Japan), and stir and mix at 2400 rpm for 30 seconds. Change the stirring speed to 4800 rpm, add 39 g of distilled water while stirring, and then stir at 4800 rpm for 60 seconds. Finally, stir at 900 rpm for 5 minutes. The obtained particles are taken out from EL-1, dried at 150 ° C for 30 minutes, and then calcined at 1,150 ° C for 1 hour to obtain a sintered body 1. For sintered body 1, ICP emission spectrometry (manufactured by Hitachi High-Technologies Corporation, SPS5520) is used to determine the element content of Si and Na, and the content of each element is converted into oxides to obtain their mass % relative to the total mass. The results are shown in Table 1.

[0492] Next, the sintered body 1 was placed in a constant temperature and humidity chamber at 25° C. and 50% humidity for 7 days, and then the water content was measured. It should be noted that after the above-mentioned placing treatment, no drying treatment was performed separately.

[0493] In a molybdenum boat in a vacuum evaporation device (ULVAC Machinery Co., Ltd., VTR-350M), 10 g of sintered body 1 was placed as the evaporation source of the base layer, and 0.5 g of compound 3A was placed as the fluorine-containing ether compound of the evaporation source of the water-repellent and oil-repellent layer. A glass substrate (AGC, Dragontrail (registered trademark)) was placed in the vacuum evaporation device, and the vacuum evaporation device was vented to 5×10 -3 Pressure below Pa.

[0494] The boat on which the granules 1 were placed was heated to 2,000° C. and vacuum-deposited onto a glass substrate to form an underlayer having a thickness of 10 nm.

[0495] The boat carrying the fluorinated ether compound was heated to 700°C, and a condensate of the fluorinated ether compound was vacuum-deposited on the base layer to form a 10 nm thick water- and oil-repellent layer. The base layer was then heat treated at 140°C for 30 minutes to obtain a glass substrate with a water- and oil-repellent layer.

[0496] (Examples 2~6)

[0497] The conditions for placing the sintered body were changed to those shown in Table 1. In Example 4, a glass substrate with a water- and oil-repellent layer was obtained in the same manner as in Example 1 except that the conditions for placing the sintered body were changed to those shown in Table 1. In Example 4, a drying treatment was performed at 200° C. for 1 hour after placing the sintered body.

[0498] (Examples 7~12)

[0499] Instead of soda ash, the raw materials listed in Table 1 were used, the oxide conversion amount of element I in the vapor deposition material was adjusted to reach the value in Table 1, and the firing temperature was adjusted. Otherwise, the same steps as in Example 1 were followed to obtain a glass substrate with a water- and oil-repellent layer.

[0500] (Examples 13~15)

[0501] A glass substrate with a water- and oil-repellent layer was obtained by the same procedure as in Example 1 except that the firing temperature when obtaining the sintered body and the conditions when the sintered body was left to stand were changed to the conditions described in Table 1.

[0502] The column "Amount of element I in the deposition material as oxide (mass %)" in Table 1 indicates the value of the content of element I in the deposition material expressed as mass % of the oxide relative to the total mass of the deposition material. For example, in the case of Example 1, the content of sodium derived from soda ash in the deposition material as oxide relative to the total mass of the deposition material is indicated (in other words, the content of sodium oxide relative to the total mass of the deposition material).

[0503] The column "Element I / Silicon (molar ratio)" in Table 1 shows the ratio of the total molar concentration of element I in the vapor deposition material to the molar concentration of silicon.

[0504] The "Storage Conditions" column in Table 1 indicates storage temperature, storage humidity, and storage time from the left. For example, "25°C, 50%, 7 days" in Example 1 indicates that the storage temperature is 25°C, the storage humidity is 50%, and the storage time is 7 days.

[0505] The column "water content" in Table 1 shows the water content of the vapor deposition material.

[0506] The column "Mass ratio" in Table 1 shows the content (mass %) of particles with a particle size of less than 0.5 mm, particles with a particle size of 0.5 to 22.4 mm, and particles with a particle size of more than 22.4 mm in the obtained vapor deposition material relative to the total mass of all particles.

[0507] The "D90 / D10" column in Table 1 indicates the ratio of D90 to D10 (D90 / D10) when the particle size when the cumulative number of particles is 10% is defined as D10, and the particle size when the cumulative number of particles is 90% is defined as D90 in the volume-based particle size distribution of the particles constituting the vapor deposition material.

[0508] [Table 1]

[0509]

[0510] It was confirmed that the vapor deposition material of the present invention can obtain the desired effect.

[0511] Industrial Applicability

[0512] The base material with water-repellent and oil-repellent layer of the present invention can be used for various purposes requiring to give water-repellent and oil-repellent.For example, it can be used for display input devices such as touch panel, transparent glass or transparent plastic components, lenses for glasses, etc., kitchen antifouling components, electronic equipment, heat exchangers, batteries, etc., water-repellent and moisture-proof components, antifouling components, antifouling components for toiletries, components that need to be turned on and liquid-repellent, components for water-repellent / waterproof / water-skiing of heat exchangers, vibrating screens, low-friction components on the surface of cylinder interior, etc. As a more specific use example, the front protection plate of the display, anti-reflection plate, polarizing plate, anti-glare plate, or the product obtained by applying anti-reflection film treatment to their surfaces, portable phones (such as smart phones), portable information terminals, game consoles, remote controllers, etc., touch panel sheets, touch panel displays, etc., have various devices (for example, glass or film used in display parts, etc., and glass or film used in the exterior decoration parts other than the display parts) of the display input device for operating on the screen with people's fingers or palms. In addition to the above, decorative building materials for water-using places such as toilets, bathrooms, washrooms, and kitchens, waterproof components for wiring boards, water-repellent / water-proof / water-slide components for heat exchangers, water-repellent components for solar cells, waterproof / water-repellent components for printed circuit boards, electronic equipment cases, waterproof / water-repellent components for electronic components, components for improving the insulation of power transmission lines, waterproof / water-repellent components for various filters, radio wave absorbing materials, waterproof components for sound-absorbing materials, anti-fouling components for bathrooms, kitchen equipment, and toiletries, low-friction components for surfaces such as vibrating screens and cylinder interiors, mechanical components, vacuum equipment components, bearing components, components for transportation equipment such as automobiles, and surface protection components for tools.

[0513] It should be noted that the entire contents of the specification, claims, abstract, and drawings of Japanese Patent Application No. 2018-242961 filed on December 26, 2018 are cited herein and incorporated as the disclosed contents of the present specification.

[0514] Description of Reference Numerals

[0515] 10 Base material with base layer

[0516] 12. Substrate

[0517] 14 Basal layer

[0518] 20 Substrate with water and oil repellent layer

[0519] 22 Substrate

[0520] 24 Basal layer

[0521] 26 Water and oil repellent layer

Claims

1. A substrate with a water-repellent and oil-repellent layer, comprising a base layer formed on a substrate and a water-repellent and oil-repellent layer formed on the base layer, The base layer is formed by vapor deposition using a vapor deposition material, and the water- and oil-repellent layer is formed by a condensate of a fluorine-containing compound having a reactive silyl group. The evaporation material includes an oxide, wherein the oxide includes silicon and at least one element selected from the group consisting of Group 1 elements, Group 2 elements, Group 13 elements, and Group 15 elements of the periodic table. The ratio of the total molar concentration of at least one element selected from the group consisting of Group 1 elements, Group 2 elements, Group 13 elements and Group 15 elements of the periodic table to the molar concentration of silicon is 0.003 to 9.0, The water content of the vapor deposition material is 2000 mass ppm or more and less than 2.0 mass %.

2. The substrate with a water- and oil-repellent layer according to claim 1, wherein In the evaporation material, a ratio of a total molar concentration of at least one element selected from the group consisting of Group 1 elements, Group 2 elements, Group 13 elements, and Group 15 elements of the periodic table to a molar concentration of silicon is 0.02 to 0.

5.

3. The substrate with a water- and oil-repellent layer according to claim 1, wherein The evaporation material is a sintered body or a molten body.

4. The substrate with a water- and oil-repellent layer according to any one of claims 1 to 3, wherein The substrate is glass.

5. A method for producing a substrate with a water- and oil-repellent layer according to any one of claims 1 to 4, wherein: By evaporation using the evaporation material, a base layer including an oxide including the silicon and the element is formed on a substrate, Next, a water- and oil-repellent layer is formed on the base layer. The water- and oil-repellent layer is formed of a condensate of a fluorine-containing compound having a reactive silyl group.

6. The method for producing a substrate with a water- and oil-repellent layer according to claim 5, wherein: The fluorine-containing compound is coated on the base layer by a dry coating method or a wet coating method and condensed.

7. The method for producing a substrate with a water- and oil-repellent layer according to claim 5 or 6, wherein: The reactive silyl group is a group represented by the following formula (2): -Yes (R) n IT 3-n …(2) Here, R is a monovalent hydrocarbon group, L is a hydrolyzable group or a hydroxyl group, and n is an integer of 0 to 2.

8. The method for producing a substrate with a water- and oil-repellent layer according to claim 5 or 6, wherein: The fluorine-containing compound is a fluorine-containing compound having two or more reactive silyl groups.

9. The method for producing a substrate with a water- and oil-repellent layer according to claim 5 or 6, wherein: The fluorine-containing compound is a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a reactive silyl group.

10. The method for producing a substrate with a water- and oil-repellent layer according to claim 9, wherein: The poly(oxyfluoroalkylene) chain is a poly(oxyfluoroalkylene) chain mainly composed of oxyperfluoroalkylene.

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