WO2020137990A1

WO2020137990A1 - Vapor deposition material, method for manufacturing substrate having underlayer thereon, and method for manufacturing substrate having water-repellent and oil-repellent layer thereon

Info

Publication number: WO2020137990A1
Application number: PCT/JP2019/050402
Authority: WO
Inventors: 万江美岩橋; 莅霖周; 広和小平; 健二石関; 小林　大介
Original assignee: Ａｇｃ株式会社
Priority date: 2018-12-26
Filing date: 2019-12-23
Publication date: 2020-07-02
Also published as: CN113227441A; JPWO2020137990A1

Abstract

Provided is a vapor deposition material that makes it possible to form an underlayer capable of uniformly forming a water-repellent and oil-repellent layer comprising a condensate of a fluorine-containing compound having a reactive silyl group, and that makes it possible to suppress variation in the underlayer composition among samples when a plurality of substrates having an underlayer thereon are prepared. The present invention provides a vapor deposition material that is composed of particles containing an oxide containing: silicon; and at least one element I 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. The mass ratio of particles having a particle size of 0.5-22.4 mm is 90 mass% or more with respect to the total mass of all particles.

Description

Vapor deposition material, method for producing base material with underlayer, method for producing base material with water/oil repellent layer

The present invention relates to a vapor deposition material, a method for producing a base material with a base layer, and a method for producing a base material with a water/oil repellent layer.

In order to impart water repellency and oil repellency, fingerprint stain removability, lubricity (smoothness when touched with fingers), etc. to the surface of the base material, surface treatment using a fluorine-containing compound having a reactive silyl group is performed. It is known to form a water/oil repellent layer made of a condensate of a fluorine-containing compound on the surface of a substrate.

Also, in order to improve the adhesion between the base material and the water/oil repellent layer, a base layer may be provided between them. Paragraph [0204] of Patent Document 1 and Paragraph [0076] of Patent Document 2 describe that an underlayer made of silicon oxide is provided between the base material and the water/oil repellent layer. These base layers are formed by vapor deposition.

JP, 2014-218639, A JP, 2012-72272, A

On the other hand, depending on the type of vapor deposition material used to form the underlayer, when an attempt is made to form a water/oil repellent layer made of a condensate of a fluorine-containing compound having a reactive silyl group on the underlayer, the water-repellent layer on the underlayer is repelled. In some cases, the water/oil repellent layer was not formed uniformly. If the water/oil repellent layer is not uniformly formed, it means that a defect area where the water/oil/oil repellent layer is not formed is formed on the underlayer, a foreign substance is observed in the water/oil repellent layer, or a foreign substance is observed in the underlayer. It means that
Moreover, when forming a base layer using a vapor deposition material, a plurality of base materials may be arranged in a vacuum vapor deposition apparatus to prepare a plurality of samples. In this way, when a plurality of samples are produced, variations in the composition of the underlayer may occur between the obtained samples. If there is a variation in the composition of the underlayer, a difference in the ease of forming the water/oil repellent layer may occur between the samples, resulting in a difference in performance.

Therefore, the present invention can form an underlayer capable of uniformly forming a water- and oil-repellent layer made of a condensate of a fluorine-containing compound having a reactive silyl group, and when producing a plurality of substrates with an underlayer. Another object of the present invention is to provide a vapor deposition material in which variation in the composition of the underlayer between samples is suppressed.
Moreover, this invention also makes it a subject to provide the manufacturing method of the base material with a base layer, and the manufacturing method of the base material with a water/oil repellent layer.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following configuration.

[1] Oxidation containing silicon and at least one element selected from the group consisting of Group 1 element, Group 2 element, Group 13 element, Group 15 element, and transition metal element of the periodic table Composed of particles containing things,
A vapor deposition material in which the mass ratio of the particles having a particle size of 0.5 to 22.4 mm is 90% by mass or more based on the total mass of all particles.

[2] In the volume-based particle size distribution of the particles constituting the vapor deposition material, the particle size when the cumulative particle number is 10% is defined as D10, and the particle size when the cumulative particle number is 90% is defined as D90. The vapor deposition material according to [1], wherein the ratio of D90 (D90/D10) to 6 is 6 or less.
[3] The vapor deposition material according to [1] or [2], which has a water content of less than 2.0% by mass.
[4] The vapor deposition material according to any one of [1] to [3], which is a sintered body or a molten body.
[5] An underlayer containing an oxide containing the silicon and the element is formed on a substrate by vapor deposition using the vapor deposition material according to any one of [1] to [4]. Of manufacturing a coated substrate.

[6] An underlayer containing an oxide containing the silicon and the element is formed on a base material by vapor deposition using the vapor deposition material described in any of [1] to [4],
Next, a method for producing a substrate with a water/oil repellent layer, which comprises forming a water/oil repellent layer comprising a condensate of a fluorine-containing compound having a reactive silyl group on the underlayer.
[7] The method for producing a substrate with a water/oil repellent layer according to [6], wherein the fluorine-containing compound is applied onto the underlayer by a dry coating method or a wet coating method and condensed.
[8] The method for producing a substrate with a water/oil repellent layer according to [6] or [7], wherein the reactive silyl group is a group represented by the following formula (2).
-Si(R) _n L _3-n ... (2)
However, R is a monovalent hydrocarbon group, L is a hydrolyzable group or a hydroxyl group, and n is an integer of 0 to 2.
[9] The method for producing a substrate with a water/oil repellent layer according to any of [6] to [8], wherein the fluorine-containing compound is a fluorine-containing compound having two or more reactive silyl groups.
[10] The substrate with a water/oil repellent layer according to any of [6] to [9], wherein the fluorine-containing compound is a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a reactive silyl group. Manufacturing method.
[11] The method for producing a substrate with a water/oil repellent layer according to [10], wherein the poly(oxyfluoroalkylene) chain is a poly(oxyfluoroalkylene) chain mainly containing an oxyperfluoroalkylene group.

According to the present invention, it is possible to form an underlayer capable of uniformly forming a water- and oil-repellent layer composed of a condensate of a fluorine-containing compound having a reactive silyl group. It is possible to provide a vapor deposition material in which variations in the composition of the underlayer between samples are suppressed.
Further, according to the present invention, it is possible to provide a method for producing a substrate with a base layer and a method for producing a substrate with a water/oil repellent layer.

It is sectional drawing which shows an example of the base material with a base layer obtained by the method of this invention. FIG. 3 is a cross-sectional view showing an example of a substrate with a water/oil repellent layer obtained by the method of the present invention.

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

In the present specification, the unit represented by the formula (1) is referred to as “unit (1)”. Units represented by other formulas are also described in the same manner. The group represented by the formula (2) is referred to as "group (2)". Groups represented by other formulas will be described in the same manner. The compound represented by the formula (3) is referred to as "compound (3)". The same applies to compounds represented by other formulas.
In the present specification, when the "alkylene group may have an A group", the alkylene group may have an A group between carbon-carbon atoms in the alkylene group, or an alkylene group- It may have an A group at the terminal such as A group-.

The meanings of the terms in the present invention are as follows.
The “divalent organopolysiloxane residue” is a group represented by the following formula. R ^x in the following formula is an alkyl group (preferably having a carbon number of 1 to 10) or a phenyl group. Further, g1 is an integer of 1 or more, preferably an integer of 1 to 9, and particularly preferably an integer of 1 to 4.

The “sylphenylene skeleton group” is a group represented by —Si(R ^y ) ₂ PhSi(R ^y ) _2- (wherein Ph is a phenylene group and R ^y is a monovalent organic group). Is. As R ^y , an alkyl group (preferably having a carbon number of 1 to 10) is preferable.
The “dialkylsilylene group” is a group represented by —Si(R ^z ) _2- (wherein R ^z is an alkyl group (preferably having a carbon number of 1 to 10)).
The “number average molecular weight” of a compound is calculated by ¹ H-NMR and ¹⁹ F-NMR to determine the number (average value) of oxyfluoroalkylene groups based on the terminal group.

Unless otherwise specified, the content of each element in the vapor deposition material is a value measured by wet analysis. The content of each element given by the wet analysis is a mass percent concentration (mass %). Atomic absorption method is used to measure Group 1 elements of the periodic table, and other elements are measured using inductively coupled plasma (ICP) emission spectroscopy or ICP mass spectrometry, and quantified by a calibration curve (matrix matching) method. To do. The ratio of the molar concentration of each element can be determined from the mass% of each element obtained by the wet analysis and the atomic weight (g/mol) of each element.
The dimensional ratios in FIGS. 1 and 2 are different from actual ones for convenience of explanation.

[Evaporation material]
The vapor deposition material of the present invention 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 of the periodic table ( Hereinafter, referred to as “element I”), and a mass ratio of particles having a particle size of 0.5 to 22.4 mm is 90 mass% or more based on the total mass of the particles. Is.
In the present invention, the vapor deposition material means a material used for vapor deposition. The vapor deposition material of the present invention is suitably used for forming a base layer in a substrate with a water/oil repellent layer described later.

The present inventors firstly found that the formation state of the underlayer contributes to the reason that the water/oil repellent layer is not uniformly formed on the underlayer. More specifically, when the underlayer is formed by vapor deposition using the vapor deposition material, a mass of the vapor deposition material is applied onto the base material to form a part of the underlayer, and the water/oil repellent layer is formed in this region. We know that it is difficult to form. Furthermore, it has been found that the distribution state of particles in the vapor deposition material is related to the reason why such a mass of the vapor deposition material occurs during vapor deposition. More specifically, it has been found that particles having a particle size of less than 0.5 mm are easily scattered as a lump during vapor deposition, and a desired effect can be obtained by reducing the proportion of such particles having a small particle size. ..
Further, they have found that variations in the composition of the underlayer are more likely to occur when the ratio of particles having a particle size of more than 22.4 mm is large and the vapor deposition material contains two or more kinds of elements other than oxygen. More specifically, first, when the hearth is filled with the vapor deposition material, if the vapor deposition material has a large particle diameter, the surface formed by the filled vapor deposition material is likely to have irregularities. When two or more kinds of elements other than oxygen of the vapor deposition material are included, the easiness of evaporation differs depending on the element during vapor deposition. Due to the unevenness and the difference in the easiness of evaporation of the elements, the easiness of the adhesion of the elements varies depending on the arrangement position of the substrate in the vacuum vapor deposition apparatus, and as a result, the composition of the underlayer between the samples varies. I know that. Therefore, by increasing the mass ratio of particles having a predetermined particle size, the ratio of particles having a particle size of more than 22.4 mm is reduced, and the above problem is solved.

The vapor deposition material is composed of particles containing a predetermined oxide described later. That is, the vapor deposition material is composed of a plurality of predetermined particles.
In the vapor deposition material, the mass ratio of particles having a particle size of 0.5 to 22.4 mm is 90 mass% or more based on the total mass of all particles, and the condensation of the fluorine-containing compound having a reactive silyl group on the underlayer. 95 because a water- and oil-repellent layer made of a substance (hereinafter, also simply referred to as “water- and oil-repellent layer”) can be formed more uniformly, or variation in the composition of the underlayer between samples is further suppressed. Mass% or more is preferable. The upper limit is 100% by mass.
The particle size of the particles corresponds to the size of each particle and means the major axis.
The method for measuring the particle size of the particles is as follows.
JIS Z8801-1 standard test sieve-Metal mesh sieve with nominal openings of 500 μm (0.5 mm) and 22.4 mm was used to screen the total number of particles and then the mass of each particle size distribution was measured. The mass ratio of each particle size is calculated.

In the volume-based particle size distribution of particles constituting the vapor deposition material, when the particle size when the cumulative particle number is 10% is defined as D10 and the particle size when the cumulative particle number is 90% is defined as D90, the ratio of D90 to D10 (D90/D10) is preferably 6.0 or less, particularly preferably 5.0 or less. If the above ratio is within the above range, it is known that variations in composition among particles during the production of particles are reduced.
The above ratio is preferably 2.0 or more.
The particle size distribution is measured by the following method.
JIS Z8801-1 standard test sieve-Metal mesh sieves having nominal openings of 300 μm, 500 μm, 1.0 mm, 4.75 mm, 9.5 mm, and 22.4 mm were used to screen all particles, and then the The mass is measured, a particle size distribution curve is prepared, and D90/D10 is calculated.

Examples of the method for adjusting the particle size and particle size distribution include a method for adjusting the production conditions for producing the vapor deposition material and a method for sieving with a mesh having a predetermined size.
More specifically, for example, a method of adjusting the size of the sintered body described later will be described below as an example. First, as a method for obtaining a sintered body, for example, a mixture of a powder containing silicon, a powder of the element I and water is dried, and then the dried mixture or this is press-molded. Examples include a method of firing a molded body to obtain a sintered body. In this method, the size of the finally obtained sintered body can be adjusted by adjusting the stirring speed and stirring time during the above mixing.

The water content of the vapor deposition material is preferably less than 2.0% by mass, more preferably 1.5% by mass or less, and 1.0% by mass from the viewpoint that the water-repellent and oil-repellent layer can be formed more uniformly on the underlayer without defects. The following are particularly preferred.
The lower limit of the water content of the vapor deposition material is, for example, 10 mass ppm or more. From the viewpoint that the adhesion of the water/oil repellent layer to the underlying layer is more excellent, 50 mass ppm or more is preferable, and 100 mass ppm or more is more preferable. 200 mass ppm or more is particularly preferable.
The method for measuring the water content of the vapor deposition material is as follows.
The vapor deposition material is placed in an environment of 300° C., and the amount of water vapor that emerges is quantified by the Karl Fischer method (coulometric titration method).

As a method of adjusting the water content of the vapor deposition material, a method of adjusting heating conditions (for example, heating temperature) in the production method of the vapor deposition material described later, a method of allowing the vapor deposition material to stand under an environment of a predetermined temperature and humidity Are listed.

The Group 1 element of the periodic table (hereinafter, also referred to as “Group 1 element”) means lithium, sodium, potassium, rubidium and cesium, and a water- and oil-repellent layer is more uniformly formed on the underlayer without defects. Lithium, sodium, and potassium are preferable, and sodium and potassium are particularly preferable, from the viewpoint that they can be formed or variation in the composition of the underlayer between samples can be further suppressed. The Group 1 element may include only one type or two or more types.
Group 2 element of the periodic table (hereinafter, also referred to as “Group 2 element”) means beryllium, magnesium, calcium, strontium, and barium, and a water- and oil-repellent layer is formed more uniformly on the underlayer without defects. Magnesium, calcium, and barium are preferable, and magnesium and calcium are particularly preferable, because they can be formed or variation in the composition of the underlayer between samples is further suppressed. The Group 2 element may include only one type or two or more types.
Group 13 element of the periodic table (hereinafter, also referred to as “Group 13 element”) means boron, aluminum, gallium, and indium, and a water/oil repellent layer can be formed more uniformly on the underlayer without defects. From the viewpoint of suppressing the variation in the composition of the underlayer between the samples, boron, aluminum and gallium are preferable, and boron and aluminum are particularly preferable. The Group 13 element may include only one type or two or more types.
Group 15 element of the periodic table (hereinafter, also referred to as “Group 15 element”) means nitrogen, phosphorus, arsenic, antimony and bismuth, and a water- and oil-repellent layer on the underlayer is more uniform without defects. Phosphorus, antimony, and bismuth are preferable, and phosphorus and bismuth are particularly preferable, because they can be formed or variation in the composition of the underlayer between samples is further suppressed. The Group 15 element may include only one type or two or more types.
The transition metal element means an element existing between the Group 3 element and the Group 11 element of the periodic table.

The oxide contained in the vapor deposition material may be a mixture of oxides of the above elements (silicon, element I) alone (for example, a mixture of silicon oxide and an oxide of element I), or 2 It may be a complex oxide containing one or more species, or may be a mixture of a complex oxide with an oxide of the above element alone.

The content of the oxide in the vapor deposition material is preferably 80% by mass or more, more preferably 95% by mass or more, with respect to the total mass of the vapor deposition material, from the viewpoint that the wear resistance of the water/oil repellent layer is more excellent. Mass% (all of the vapor deposition material is an oxide) is particularly preferable.
The content of oxygen in the vapor deposition material is preferably 40 to 70 mol% as the molar concentration (mol %) of oxygen with respect to all the elements in the vapor deposition material, from the viewpoint of more excellent abrasion resistance of the water/oil repellent layer, and 50 ˜70 mol% is more preferred, and 60˜70 mol% is particularly preferred. The content of oxygen in the vapor deposition material is measured by XPS analysis or the like for the pelletized vapor deposition material that has been sufficiently pulverized.

The content of silicon in the vapor deposition material is 10 to 99.8 mol as the molar concentration (mol %) of silicon with respect to all elements other than oxygen in the vapor deposition material from the viewpoint that the abrasion resistance of the water/oil repellent layer is more excellent. % Is preferable, 15 to 99.8 mol% is more preferable, and 20 to 99.7 mol% is particularly preferable.
The content of silicon in the vapor deposition material is 10 to 99.9 in terms of the abrasion resistance of the water/oil repellent layer as the mass percent concentration (mass %) of silicon with respect to all elements except oxygen in the vapor deposition material. Mass% is preferable, 20 to 99.9 mass% is more preferable, and 30 to 99.8 mass% is particularly preferable.

The ratio of the total molar concentration of the element I to the molar concentration of silicon in the vapor deposition material is preferably 0.003 to 9.0, and more preferably 0.003 to 9.0, from the viewpoint that the abrasion resistance of the water/oil repellent layer is more excellent. 0 is more preferable, and 0.003 to 0.5 is particularly preferable.
When the content of the element I in the vapor deposition material is within the above range, the underlayer can be stably formed on the surface of the base material by the vapor deposition method, and defects due to scattering of the vapor deposition material hardly occur in the underlayer. As a result, the adhesiveness between the underlayer and the water/oil repellent layer is excellent, and the abrasion resistance of the water/oil repellent layer is excellent, which is preferable.

The total content of the element I in the vapor deposition material is expressed in mass% based on the oxide, and is preferably 0.5 mass% or more, and particularly preferably 1 mass% or more, based on the total mass of the vapor deposition material. When the content of the element I is within the above range, the underlayer can be stably formed on the surface of the substrate by the vapor deposition method, and defects due to scattering of the vapor deposition material are unlikely to occur in the underlayer. As a result, the adhesiveness between the underlayer and the water/oil repellent layer is excellent, and the abrasion resistance of the water/oil repellent layer is excellent, which is preferable. The upper limit is 95% by mass.

The total content of the element I in the vapor deposition material is the total mass percent concentration (mass %) of the element I with respect to all the elements other than oxygen in the vapor deposition material, because the abrasion resistance of the water/oil repellent layer is more excellent, 0.001 to 90 mass% is preferable, 0.001 to 80 mass% is more preferable, and 0.001 to 70 mass% is particularly preferable.
When the content of the element I in the vapor deposition material is within the above range, the Si—O—Si bond is sufficiently formed in the underlayer, the mechanical properties of the underlayer are sufficiently ensured, and the abrasion resistance of the water/oil repellent layer is improved. It is excellent because it is preferable.

The vapor deposition material may contain, as the element I, one kind of the above-mentioned elements or two or more kinds thereof. When two or more elements are contained, the total content of two or more elements satisfies the above range.

Specific examples of the form of the vapor deposition material include a powder, a melt, a sintered body, a granulated body, and a crushed body, and the sintered body and the melted body are preferable because the water content can be easily adjusted.
Here, the term "sintered body" refers to a solid material obtained by firing powder of an evaporation material, and if necessary, a powder is pressed to form a molded body instead of the powder of the evaporation material. May be used. The melt means a solid obtained by melting powder of the vapor deposition material at high temperature and then cooling and solidifying the powder. The granulated material means a solid material obtained by kneading a powder of a vapor deposition material and a liquid medium (for example, water, an organic solvent) to obtain particles, and then drying the particles.

The vapor deposition material can be manufactured, for example, by the following method.
A method of obtaining powder of vapor deposition material by mixing powder of oxide of silicon and powder of oxide of element I.
A method of kneading the powder of the vapor deposition material and water to obtain particles and then drying the particles to obtain a granule of the vapor deposition material.
The diameter of the raw material silicon oxide powder is preferably 0.1 μm to 100 μm in order to increase the yield during granulation and to make the element distribution in the granule uniform. When using a silicon oxide powder having a particle size of 100 μm or more as a raw material, it is preferable to use it after pulverizing. The drying temperature is preferably 60° C. or higher in order to increase the strength of the granulated body and to avoid sticking during firing when obtaining the sintered body. On the other hand, in order to completely remove water, drying under reduced pressure (absolute pressure of 50 kPa or less) is preferable.
A mixture obtained by mixing powder containing silicon (for example, powder made of oxide of silicon, silica sand, silica gel), powder of element I (for example, powder of oxide of element I), and water. After drying, the mixture after drying, the molded body obtained by press molding the mixture, or the granulated body is fired to obtain a sintered body.
In order to reduce the hygroscopicity of the sintered body after firing, the firing temperature is preferably 900°C or higher, more preferably 1000°C or higher. In order to prevent damage to the transport container (packaging bag) during transportation of the sintered body and to prevent contamination from the container, particles without protrusions are preferable, and spherical particles are more preferable. It is preferred to add a protrusion removal process to remove the protrusions.
After melting powder containing silicon (for example, powder made of oxide of silicon, silica sand, silica gel) and powder of element I (for example, powder of oxide of element I) at high temperature , A method of obtaining a melt by cooling and solidifying a melt.

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.
For example, in the method for obtaining a sintered body, the firing temperature for firing is preferably 300°C or higher, and particularly preferably 500°C or higher. The upper limit of the firing temperature is 2000° C. or lower.

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

A vacuum vapor deposition method is mentioned as a specific example of the vapor deposition method using a vapor deposition material. 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 base material.
The temperature during vapor deposition (for example, when using a vacuum vapor deposition apparatus, the temperature of the boat on which the vapor deposition material is installed) is preferably 100 to 3000°C, and particularly preferably 500 to 3000°C.
The pressure during vapor deposition (for example, when using a vacuum vapor deposition apparatus, the pressure in the tank in which the vapor deposition material is placed) is preferably 1 Pa or less, and particularly preferably 0.1 Pa or less.
When the underlayer 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.

Specific examples of the vaporization method of the vapor deposition material include a resistance heating method of melting and vaporizing the vapor deposition material on a high-melting-point metal resistance heating boat, irradiating the vapor deposition material with an electron beam, and directly heating the vapor deposition material to the surface. There is an electron gun method of melting and evaporating. As a method of vaporizing the vapor deposition material, the high melting point substance can be vaporized because it can be locally heated, and since the place where the electron beam is not hit is low temperature, there is no risk of reaction with the container or mixing of impurities. The gun method is preferred.
At the time of vapor deposition, in order to prevent contamination of regions or portions that are not desired to be vapor-deposited (for example, the back surface of the substrate), a method of covering the regions or portions that are not desired to be vapor-deposited with a protective film can be mentioned. ..
After vapor deposition, it is preferable to add a humidification treatment from the viewpoint of improving the 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.

FIG. 1 is a cross-sectional view schematically showing an example of a substrate with an underlayer produced by the method of the present invention. The base material 10 with a base layer includes a base material 12 and a base material layer 14 formed on one surface of the base material 12.
In the example of FIG. 1, the base material 12 and the base layer 14 are in contact with each other, but the base material with the base layer is not limited to this. May have.
In the example of FIG. 1, the base layer 14 is formed on the entire one surface of the base material 12, but the present invention is not limited to this, and the base layer 14 is formed only in a partial region of the base material 12. Good.
In the example of FIG. 1, the base layer 14 is formed only on one surface of the base material 12, but the present invention is not limited to this, and the base layer 14 may be formed on both surfaces of the base material 12.

(Base material)
As the base material, a water- and oil-repellent property can be imparted, and therefore, a substrate for which water- and oil-repellency property is required is particularly preferable. Specific examples of the material of the base material include metals, resins, glasses, sapphires, ceramics, stones, and composite materials thereof. The glass may be chemically strengthened.
As the substrate, a touch panel substrate and a display substrate are preferable, and a touch panel substrate is particularly preferable. The touch panel substrate preferably has a light-transmitting property. "Has translucency" means that the vertical incidence type visible light transmittance according to JIS R3106: 1998 (ISO 9050: 1990) is 25% or more. As the material of the touch panel substrate, glass and transparent resin are preferable.
Examples of the base material include the following. Used for building materials, decorative building materials, interior goods, transportation equipment (eg automobiles), signboards/bulletins, drinking vessels/tableware, aquariums, ornamental equipment (eg foreheads, boxes), laboratory equipment, furniture, art/sports/games Yes, glass or resin products. Glass products or resin products used for exterior parts (excluding the display section) of devices such as mobile phones (eg smartphones), personal digital assistants, game consoles, remote controllers, etc.
The shape of the base material may be a plate shape or a film shape.

The base material may be a base material having one surface or both surfaces subjected to surface treatment such as corona discharge treatment, plasma treatment, and plasma graft polymerization treatment. The surface-treated surface has more excellent adhesion between the base material and the underlayer, and as a result, more excellent abrasion resistance of the water/oil repellent layer. Therefore, it is preferable to perform a surface treatment on the surface of the base material that is in contact with the underlayer.

(Underlayer)
The underlayer contains an oxide containing at least silicon and element I.
The oxide contained in the underlayer may contain, as the element I, one kind of the above-mentioned elements or two or more kinds thereof.

The oxide contained in the underlayer may be a mixture of oxides of the above-mentioned elements (silicon and element I) alone (for example, a mixture of silicon oxide and an oxide of element I). It may be a complex oxide containing a compound or a mixture of a complex oxide and an oxide of the above-mentioned element alone.

The underlayer is a layer in which the contained components are uniformly distributed (hereinafter, also referred to as “homogeneous layer”), but a layer in which the contained components are unevenly distributed (hereinafter, also referred to as “heterogeneous layer”). ). As a specific example of a heterogeneous layer, when a concentration gradient of components (horizontal direction or vertical direction of the surface formed by the layer) occurs in the layer (gradient structure), discontinuous in the components that exist continuously When other components are present in (sea-island structure).
The underlayer may be a single layer or multiple layers, but a single layer is preferable from the viewpoint that the water- and oil-repellent layer is more excellent in abrasion resistance.

The thickness of the underlayer is preferably 1 to 100 nm, more preferably 1 to 50 nm, particularly preferably 2 to 20 nm. When the thickness of the underlayer is at least the above lower limit, the adhesion of the water/oil repellent layer by the underlayer is further improved, and the abrasion resistance of the water/oil repellent layer is more excellent. When the thickness of the underlayer is not more than the above upper limit, the abrasion resistance of the underlayer itself is excellent.
The thickness of the underlayer is measured by observing a cross section of the underlayer with a transmission electron microscope (TEM).

[Method for producing base material with water/oil repellent layer]
The method for producing a substrate with a water/oil repellent layer of the present invention is, as described in the method for producing a substrate with an underlayer of the present invention, a method of depositing silicon on the substrate by a vapor deposition method using the vapor deposition material of the present invention. A method of forming an underlayer containing an oxide containing the element I and then forming a water/oil repellent layer made of a condensate of a fluorine-containing compound having a reactive silyl group on the underlayer.

The water- and oil-repellent layer can be formed using a fluorine-containing compound or a composition containing a fluorine-containing compound and a liquid medium (hereinafter, also referred to as “composition”) by either a dry coating method or a wet coating method.
Specific examples of the liquid medium contained in the composition include water and organic solvents. Specific examples of the organic solvent include a fluorine-based organic solvent and a non-fluorine-based organic solvent. The organic solvent may be used alone or in combination of two or more.

Specific examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
The fluorinated alkane is preferably a compound having 4 to 8 carbon atoms, and examples thereof include C ₆ F ₁₃ H (AC-2000: product name, manufactured by AGC Co.), C ₆ F ₁₃ C ₂ H ₅ (AC-6000: product name). , manufactured by AGC _{_{_{Corp.), C 2 F 5 CHFCHFCF 3}}} ( Vertrel: product name, manufactured by DuPont).
Specific examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, 1,3-bis(trifluoromethyl)benzene, and 1,4-bis(trifluoromethyl)benzene.
The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms, and examples thereof include CF ₃ CH ₂ OCF ₂ CF ₂ H (AE-3000: product name, manufactured by AGC), C ₄ F ₉ OCH ₃ (Novec-7100: Product name, 3M company), C ₄ F ₉ OC ₂ H ₅ (Novec-7200: product name, 3M company), C ₂ F ₅ CF(OCH ₃ )C ₃ F ₇ (Novec-7300: product name, 3M).
Specific examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
Specific examples of fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

The non-fluorine-based organic solvent is preferably a compound consisting only of hydrogen atoms and carbon atoms, and a compound consisting only of hydrogen atoms, carbon atoms and oxygen atoms, specifically, a hydrocarbon-based organic solvent, a ketone-based organic solvent , Ether organic solvents, ester organic solvents, alcohol organic solvents.
Specific examples of the hydrocarbon-based organic solvent include hexane, heptane, and cyclohexane.
Specific examples of the ketone-based organic solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
Specific examples of the ether-based organic solvent include diethyl ether, tetrahydrofuran and tetraethylene glycol dimethyl ether.
Specific examples of the ester organic solvent include ethyl acetate and butyl acetate.
Specific examples of the alcohol-based organic solvent include isopropyl alcohol, ethanol and n-butanol.

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

The water/oil repellent layer can be produced, for example, by the following method.
A method of forming a water/oil repellent layer on the surface of the underlayer by treating the surface of the underlayer by a dry coating method using a fluorine-containing compound.
A method of applying a composition to the surface of the underlayer by a wet coating method and drying the composition to form a water/oil repellent layer on the surface of the underlayer.

Specific examples of the dry coating method include vacuum deposition method, CVD method, and sputtering method. Among these, the vacuum vapor deposition method is preferable from the viewpoint of suppressing decomposition of the fluorine-containing compound and the simplicity of the apparatus. At the time of vacuum deposition, a pellet-like substance obtained by supporting a fluorine-containing compound on a metal porous body such as iron or steel, or impregnating a composition and drying it may be used.

Specific examples of the wet coating method include a spin coating method, a wipe coating method, a spray coating method, a squeegee coating method, a dip coating method, a die coating method, an inkjet method, a flow coating method, a roll coating method, a casting method, and a Langmuir-Blodgett. Method and gravure coating method.

In order to improve the wear resistance of the water/oil repellent layer, an operation for promoting the reaction between the fluorine-containing compound having a reactive silyl group and the underlayer may be carried out, if necessary. Examples of the operation include heating, humidification, and light irradiation. For example, by heating a substrate with an underlayer on which a water/oil repellent layer is formed in an atmosphere containing water, a hydrolysis reaction of a reactive silyl group to a silanol group, a siloxane bond formation by a condensation reaction of a silanol group, A reaction such as a condensation reaction between the silanol group on the surface of the underlayer and the silanol group of the fluorine-containing compound can be promoted.
After the surface treatment, compounds in the water/oil repellent layer which are not chemically bonded to other compounds or the silicon oxide layer may be removed as necessary. Specific methods include, for example, a method of pouring a solvent on the water/oil repellent layer, a method of wiping with a cloth soaked with a solvent, and a method of washing the surface of the water/oil repellent layer with an acid.

FIG. 2 is a cross-sectional view schematically showing an example of a water-repellent/oil-repellent layer-provided substrate produced by the method of the present invention. The base material 20 with a water/oil repellent layer has a base material 22, a base layer 24 formed on one surface of the base material 22, and a water/oil repellent layer 26 formed on the surface of the base layer 24.
Further, in the example of FIG. 2, the water/oil repellent layer 26 is formed on the entire surface of the underlayer 24, but the present invention is not limited to this, and the water/oil repellent layer 26 is formed only in a part of the underlayer 24. It may be formed.
In the example of FIG. 2, the base layer 24 and the water/oil repellent layer 26 are formed only on one surface of the base material 22, but the present invention is not limited to this, and the base layer 24 and the water repellent layer are formed on both surfaces of the base material 22. The oil repellent layer 26 may be formed.

(Water and oil repellent layer)
The water/oil repellent layer is composed of a condensate of a fluorine-containing compound having a reactive silyl group.
The reactive silyl group means a hydrolyzable silyl group and a silanol group (Si—OH). Specific examples of the hydrolyzable silyl group include groups in which L of the group represented by the formula (2) described below is a hydrolyzable group.
The hydrolyzable silyl group becomes a silanol group represented by Si—OH by the hydrolysis reaction. The silanol group further undergoes a dehydration condensation reaction between the silanol groups to form a Si—O—Si bond. Further, the silanol group can form a Si—O—Si bond by a dehydration condensation reaction with a silanol group derived from an oxide contained in the underlayer. That is, when at least a part of the reactive silyl group is a hydrolyzable silyl group, the water/oil repellent layer contains a condensate obtained by subjecting the reactive silyl group of the fluorine-containing compound to a hydrolysis reaction and a dehydration condensation reaction. When all of the reactive silyl groups are silanol groups, the water/oil repellent layer contains a condensate obtained by dehydration condensation reaction of the silanol groups of the fluorine-containing compound. At least a part of the reactive silyl group contained in the fluorine-containing compound is preferably a hydrolyzable silyl group.

The thickness of the water/oil repellent layer is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. When the thickness of the water/oil repellent layer is at least the lower limit value, the effect of the water/oil repellent layer can be sufficiently obtained. When the thickness of the water/oil repellent layer is equal to or less than the above upper limit, the utilization efficiency is high.
The thickness of the water/oil repellent layer can be calculated by obtaining an interference pattern of reflected X-rays by the X-ray reflectance method (XRR) using an X-ray diffractometer for thin film analysis, and from the vibration cycle of this interference pattern.

<Fluorine-containing compound having reactive silyl group>
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/oil repellency of the water/oil repellent layer.

The poly(oxyfluoroalkylene) chain contains a plurality of units represented by formula (1).
(OX) ・・・(1)

X is a fluoroalkylene group having one or more fluorine atoms.
The carbon number of the fluoroalkylene group is preferably 2 to 6 and particularly preferably 2 to 4 from the viewpoint of more excellent weather resistance and corrosion resistance of the water/oil repellent layer.
The fluoroalkylene group may be linear or branched, but linear is preferable from the viewpoint of more excellent effect of the present invention.
The number of fluorine atoms in the fluoroalkylene group is preferably 1 to 2 times the number of carbon atoms, and particularly preferably 1.7 to 2 times, from the viewpoint of more excellent corrosion resistance of the water/oil repellent layer.
The fluoroalkylene group may be a group in which all hydrogen atoms in the fluoroalkylene group are replaced with fluorine atoms (perfluoroalkylene group).

Specific examples of the unit _{_{_{(1), -OCHF -, -}}} OCF 2 CHF -, - OCHFCF 2 -, - OCF 2 CH 2 -, - OCH 2 CF 2 -, - OCF 2 CF 2 CHF -, - OCHFCF 2 CF ₂ —, —OCF ₂ CF ₂ CH ₂ —, —OCH ₂ CF ₂ CF ₂ —, —OCF ₂ CF ₂ CF ₂ CH ₂ —, —OCH ₂ CF ₂ CF ₂ CF ₂ —, —OCF ₂ CF ₂ CF ₂ CF ₂ CH ₂ —, —OCH ₂ CF ₂ CF ₂ CF ₂ CF ₂ —, —OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ —, —OCH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ —, _{_{_{_{-OCF 2 -, - OCF 2 CF}}}} 2 -, - OCF 2 CF 2 CF 2 -, - OCF (CF 3) CF 2 -, - OCF 2 CF 2 CF 2 CF 2 -, - OCF (CF 3) CF 2 CF ₂ −, —OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ —, and —OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ — may be mentioned.

The repeating number m of the unit (1) contained in the poly(oxyfluoroalkylene) chain is 2 or more, more preferably an integer of 2 to 200, further preferably an integer of 5 to 150, particularly preferably an integer of 5 to 100. Preferably, an integer of 10 to 50 is most preferable.
The poly(oxyfluoroalkylene) chain may include two or more types of units (1). The two or more units (1) include, for example, two or more units (1) having different carbon numbers, or two or more units having the same carbon number but having different side chains or different side chains. (1), and two or more kinds of units (1) having the same number of carbon atoms but different numbers of fluorine atoms.
The bonding order of two or more types of (OX) is not limited, and they may be arranged randomly, alternately, or in blocks.
The poly(oxyfluoroalkylene) chain is preferably a poly(oxyfluoroalkylene) chain mainly containing the unit (1) which is an oxyperfluoroalkylene group in order to form a film having excellent fingerprint stain removability. In the poly(oxyfluoroalkylene) chain represented by (OX) _m , the ratio of the number of units (1) which are oxyperfluoroalkylene groups to the total number m of units (1) is 50 to 100%. It is more preferably 80 to 100%, particularly preferably 90 to 100%.
Examples of the poly(oxyfluoroalkylene) chain include a poly(oxyperfluoroalkylene) chain and a poly(oxyperfluoroalkylene) chain having one or two oxyfluoroalkylene units each having a hydrogen atom at one or both ends. More preferable.

_{Examples of} (OX) _m _{contained in the} poly(oxyfluoroalkylene) chain include (OCH _ma F _(2-ma) ) _m11 (OC ₂ H _mb F _(4-mb) ) _m12 (OC ₃ H _mc F _{(6-mc _{_{_{)) m13 (OC 4 H md}}}} F (8-md)) m14 (OC 5 H me F (10-me)) m15 (OC 6 H mf F (12-mf)) m16 is preferred.
ma is 0 or 1, mb is an integer of 0 to 3, mc is an integer of 0 to 5, md is an integer of 0 to 7, me is an integer of 0 to 9, and mf is It is an integer from 0 to 11.
m11, m12, m13, m14, m15 and m16 are each independently an integer of 0 or more, and preferably 100 or less.
m11+m12+m13+m14+m15+m16 is an integer of 2 or more, preferably an integer of 2 to 200, more preferably an integer of 5 to 150, still more preferably an integer of 5 to 100, particularly preferably an integer of 10 to 50.
Among them, m12 is preferably an integer of 2 or more, and particularly preferably an integer of 2 to 200.
In addition, C ₃ H _mc F _(6-mc) , C ₄ H _md F _(8-md) , C ₅ H _me F _(10-me) and C ₆ H _mf F _(12-mf) are linear. Or a branched chain may be used, and a linear chain is preferable from the viewpoint of more excellent abrasion resistance of the water/oil repellent layer.

The above formula represents the type and number of units, and does not represent the array of units. That is, m11 to m16 represent the number of units, and, for example, (OCH _ma F _(2-ma) ) _m11 represents a block in which (OCH _ma F _(2-ma) ) units are continuous in m11 units. is not. Similarly, the order of description of (OCH _ma F _(2-ma) ) to (OC ₆ H _mf F _(12-mf) ) does not mean that they are arranged in the order of description.
In the above formula, when two or more of m11 to m16 are not 0 (that is, (OX) _m is composed of two or more units), the different units are arranged in a random arrangement, an alternating arrangement, a block arrangement, and Any combination of those sequences may be used.
Furthermore, each unit may also be different if it contains two or more units. For example, when m11 is 2 or more, a plurality of (OCH _ma F _(2-ma) ) may be the same or different.

As the reactive silyl group, a group represented by the formula (2) is preferable.
-Si(R) _n L _3-n ... (2)

The number of the group (2) contained in the fluorine-containing ether compound is 1 or more, and 2 or more is preferable, 2 to 10 is more preferable, and 2 to 10 is preferable because the water- and oil-repellent layer has more excellent abrasion resistance. Five is more preferable, and 2 or 3 is particularly preferable.
When a plurality of groups (2) are present in one molecule, the plurality of groups (2) may be the same or different. From the viewpoint of easy availability of raw materials and easy production of the fluorine-containing ether compound, it is preferable that they are the same.

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

L is a hydrolyzable group or a hydroxyl group.
The hydrolyzable group is a group that becomes a hydroxyl group by a hydrolysis reaction. That is, the hydrolyzable silyl group represented by Si-L becomes a silanol group represented by Si-OH by the hydrolysis reaction. The silanol groups further react between the silanol groups to form Si-O-Si bonds. Further, the silanol group can form a Si—O—Si bond by a dehydration condensation reaction with the silanol group derived from the oxide contained in the underlayer.

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 preferable. The aryloxy group is preferably an aryloxy group having 3 to 10 carbon atoms. However, the aryl group of the aryloxy group includes a heteroaryl group. The halogen atom is preferably a chlorine atom. As the acyl group, an acyl group having 1 to 6 carbon atoms is preferable. As the acyloxy group, an acyloxy group having 1 to 6 carbon atoms is preferable.
As L, an alkoxy group having 1 to 4 carbon atoms and a halogen atom are preferable because the production of a fluorine-containing ether compound is easier. As L, an alkoxy group having 1 to 4 carbon atoms is preferable from the viewpoints of less outgas at the time of application and more excellent storage stability of the fluorine-containing ether compound, and when long-term storage stability of the fluorine-containing ether compound is required. In particular, an ethoxy group is particularly preferable, and a methoxy group is particularly preferable when the reaction time after coating is short.

n is an integer of 0 to 2.
n is preferably 0 or 1, and 0 is particularly preferable. The presence of a plurality of Ls makes the water- and oil-repellent layer more adherent.
When n is 1 or less, a plurality of L existing in one molecule may be the same or different. From the viewpoint of easy availability of raw materials and easy production of the fluorine-containing ether compound, it is preferable that they are the same. When n is 2, a plurality of Rs present in one molecule may be the same or different. From the viewpoint of easy availability of raw materials and easy production of the fluorine-containing ether compound, it is preferable that they are the same.

As the fluorine-containing ether compound, the compound represented by the formula (3) is preferable because it is more excellent in water and oil repellency and abrasion resistance of the water and oil repellent layer.
[A-(OX) _m -O-] _j Z[-Si(R) _n L _3-n ] _g ... (3)

A is a perfluoroalkyl group or a _{_{-Q [-Si (R) n L}} 3-n] k.
The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, and particularly preferably 1 to 3 from the viewpoint that the water- and oil-repellent layer is more excellent in abrasion resistance.
The perfluoroalkyl group may be linear or branched.
However, when A is _{_{-Q [-Si (R) n L}} 3-n] k, j is 1.

Examples of the perfluoroalkyl group include CF ₃ —, CF ₃ CF ₂ —, CF ₃ CF ₂ CF ₂ —, CF ₃ CF ₂ CF ₂ CF ₂ —, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ —, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ —, CF ₃ CF(CF ₃ )— and the like can be mentioned.
As the perfluoroalkyl group, CF ₃ —, CF ₃ CF ₂ —, and CF ₃ CF ₂ CF ₂ — are preferable because the water and oil repellent layer is more excellent in water and oil repellency.

Q is a (k+1)-valent linking group. As described later, k is an integer of 1-10. Therefore, examples of Q include a divalent to 11-valent linking group.
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 which may have an etheric oxygen atom or a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, and a silicon atom. And a divalent to octavalent organopolysiloxane residue, and groups (g2-1) to (g2-9) and groups (g3-1) to (g3-9).

Definitions of R, L, n, X and m are as described above.

Z is a (j+g)-valent linking group.
Z may be a group which does not impair the effects of the present invention, and examples thereof include an alkylene group which may have an etheric oxygen atom or a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, a silicon atom, Examples thereof include a divalent to octavalent organopolysiloxane residue, and groups (g2-1) to (g2-9) and groups (g3-1) to (g3-9).

j is an integer of 1 or more, preferably an integer of 1 to 5 from the viewpoint that the water/oil repellent layer is more excellent in water/oil repellency, and particularly preferably 1 from the viewpoint of easy production of the compound (3).
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 more excellent abrasion resistance of the water/oil repellent layer.

As the compound (3), the compound (3-11), the compound (3-21) and the compound (3-31) are preferable because they are more excellent in the initial water contact angle and the abrasion resistance of the water/oil repellent layer. Among these, the compound (3-11) and the compound (3-21) are particularly excellent in the initial water contact angle of the water/oil repellent layer, and the compound (3-31) is particularly excellent in the abrasion resistance of the water/oil repellent layer. ..

R ^f1 -(OX) _m -OY ¹¹ [-Si(R) _n L _3-n ] _g1 ... (3-11)
[R ^f2- (OX) _m -O-] _j2 Y ²¹ [-Si(R) _n L _3-n ] _g2 (3-21)
_{_{_{^{[L 3-n (R)}}}} n Si-] k3 Y 32 - (OX) m -O-Y 31 [-Si (R) n L 3-n] g3 ··· (3-31)

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.
R ^f1 is a perfluoroalkyl group, and preferred embodiments and specific examples of the perfluoroalkyl group are as described above.
Y ¹¹ is a (g1+1)-valent linking group, and specific examples thereof are the same as Z in the formula (3).
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, more preferably 2 or 3, and 3 is 3 from the viewpoint that the water- and oil-repellent layer is more excellent in abrasion resistance. Particularly preferred.

In formula (3-21), X, m, R, n and L have the same definitions as X, m, R, n and L in formula (3).
R ^f2 is a perfluoroalkyl group, and preferred embodiments and specific examples of the perfluoroalkyl group are as described above.
j2 is an integer of 2 or more, preferably an integer of 2 to 6, and more preferably an integer of 2 to 4.
Y ²¹ is a (j2+g2)-valent linking group, and specific examples thereof are the same as Z in the formula (3).
g2 is an integer of 2 or more, and is preferably an integer of 2 to 15, more preferably 2 to 6, still more preferably 2 to 4 and particularly preferably 4 from the viewpoint that the abrasion resistance of the water/oil repellent layer is more excellent. ..

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.
k3 is an integer of 1 or more, preferably an integer of 1 to 4, more preferably 2 or 3, and particularly preferably 3.
Y ³² is a (k3+1)-valent linking group, and specific examples thereof are the same as Q in formula (3).
Y ³¹ is a (g3+1)-valent linking group, and specific examples thereof are the same as Z in formula (3).
g3 is an integer of 1 or more, preferably an integer of 1 to 4, more preferably 2 or 3, and particularly preferably 3.

Y ¹¹ in the formula (3-11) is a group (g2-1) (where d1+d3=1 (that is, d1 or d3 is 0), g1=d2+d4, d2+d4≧2) and a group ( g2-2) (provided that e1=1, g1=e2, and e2≧2), group (g2-3) (provided that g1=2), group (g2-4) (provided that h1 =1, g1=h2, h2≧2), a group (g2-5) (where i1=1, g1=i2, i2≧2), a group (g2-7) (where g1) =i3+1), a group (g2-8) (where g1=i4, i4≧2), or a group (g2-9) (where g1=i5, i5≧2). May be
Y ²¹ in the formula (3-21) is a group (g2-1) (provided that j2=d1+d3, d1+d3≧2, g2=d2+d4, d2+d4≧2) and a group (g2-2) (provided that j2). =e1, e1=2, g2=e2, e2=2), the group (g2-4) (provided that j2=h1, h1≧2, g2=h2, h2≧2), or It may be a group (g2-5) (provided that j2=i1, i1=2, g2=i2, i2=2).
Further, Y ³¹ and Y ³² in the formula (3-31) are each independently a group (g2-1) (where g3=d2+d4 and k3=d2+d4) and a group (g2-2) (where g3). =e2, k3=e2), a group (g2-3) (where g3=2, k3=2), a group (g2-4) (where g3=h2, k3=h2). .), a group (g2-5) (where g3=i2 and k3=i2), a group (g2-6) (where g3=1 and k3=1) and a group (g2-7. ) (Provided that g3=i3+1 and k3=i3+1), the group (g2-8) (provided that g3=i4 and k3=i4), or the group (g2-9) (provided that g3= i5 and k3=i5).

(-A ¹ -) _e1 C(R ^e2 ) _4-e1-e2 (-Q ²² -) _e2 ...(g2-2)
-A ¹ -N(-Q ²³ -) ₂ ...(g2-3)
(-A ¹ -) _h1 Z ¹ (-Q ²⁴ -) _h2 ... (g2-4)
(-A ¹ -) _i1 Si(R ^e3 ) _4-i1-i2 (-Q ²⁵ -) _i2 ...(g2-5)
-A ¹ -Q ²⁶ -... (g2-6)
-A ¹ -CH(-Q ²² -)-Si(R ^e3 ) _3-i3 (-Q ²⁵ -) _i3 ...(g2-7)
-A ¹ -[CH ₂ C(R ^e4 )(-Q ²⁷ -)] _i4 -R ^e5 ...(g2-8)
-A ¹ -Z ^a (-Q ²⁸ -) _i5 ...(g2-9)

However, in formulas (g2-1) to (g2-9), the A ¹ side is connected to (OX) _m , and the Q ²² , Q ²³ , Q ²⁴ , Q ²⁵ , Q ²⁶ , Q ^27, and Q ²⁸ sides are [-Si(R) _n L _3-n ].

A ¹ is a single bond, an alkylene group, or —C(O)NR ⁶ —, —C(O)—, —OC(O)O—, — between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms. A group having NHC(O)O—, —NHC(O)NR ⁶ —, —O— or —SO ₂ NR ⁶ —, and in each formula, when A ¹ is 2 or more, 2 or more A ¹ May be the same or different. The hydrogen atom of the alkylene group may be substituted with a fluorine atom.
Q ²² is an alkylene group, a group having —C(O)NR ⁶ —, —C(O)—, —NR ⁶ — or —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, alkylene A group having —C(O)NR ⁶ —, —C(O)—, —NR ⁶ — or —O— at the end of the group not connected to Si, or carbon-carbon of an alkylene group having 2 or more carbon atoms -C between atoms ^{(O) NR 6 -, -} C (O) -, - NR 6 - or -O- and having and -C to the end on the side not connected to the ^{Si (O) NR 6 -,} - C (O)—, —NR ⁶ — or —O—, and in each formula, when two or more Q ^22's are present, the two or more Q ^22's may be the same or different.
Q ²³ is an alkylene group or a group having —C(O)NR ⁶ —, —C(O)—, —NR ⁶ — or —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms. Yes, the two Q ²³ may be the same or different.
Q ²⁴ is Q ²² when the atom in Z ¹ to which Q ²⁴ binds is a carbon atom, and Q ²³ when the atom in Z ¹ to which Q ²⁴ binds is a nitrogen atom, and in each formula, Q ²⁴ When two or more are present, two or more Q ²⁴ may be the same or different.
Q ²⁵ is an alkylene group or a group having —C(O)NR ⁶ —, —C(O)—, —NR ⁶ — or —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms. In each formula, when two or more Q ^{25 s} are present, the two or more Q ^{25 s} may be the same or different.
Q ²⁶ is an alkylene group or a group having —C(O)NR ⁶ —, —C(O)—, —NR ⁶ — or —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms. is there.
R ⁶ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group.
Q ²⁷ is a single bond or an alkylene group.
Q ²⁸ is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between the carbon atoms of the alkylene group having 2 or more carbon atoms.

Z ¹ is a group having an h1+h2 valent ring structure having a carbon atom or a nitrogen atom to which A ¹ is directly bonded and having a carbon atom or a nitrogen atom to which Q ²⁴ is directly bonded.

R ^e1 is a hydrogen atom or an alkyl group, and in each formula, when two or more R ^e1 are present, two or more R ^e1 may be the same or different.
R ^e2 is a hydrogen atom, a hydroxyl group, an alkyl group or an acyloxy group.
R ^e3 is an alkyl group.
R ^e4 is a hydrogen atom or an alkyl group, and is preferably a hydrogen atom from the viewpoint of easy production of a compound. In each formula, when present the R ^e4 2 or more, 2 or more R ^e4 may be the be the same or different.
R ^e5 is a hydrogen atom or a halogen atom, and is preferably a hydrogen atom from the viewpoint of easy production of a compound.

d1 is an integer of 0 to 3, preferably 1 or 2. d2 is an integer of 0 to 3, preferably 1 or 2. d1+d2 is an integer of 1 to 3.
d3 is an integer of 0 to 3, preferably 0 or 1. d4 is an integer of 0 to 3, preferably 2 or 3. d3+d4 is an integer of 1 to 3.
d1+d3 is an integer of 1 to 5 in Y ¹¹ or Y ²¹ , is preferably 1 or 2, and is 1 in Y ¹¹ , Y ³¹ and Y ³² .
d2+d4 is an integer of 2 to 5 for Y ¹¹ or Y ²¹ , preferably 4 or 5, and an integer of 3 to 5 for Y ³¹ and Y ³² , and preferably 4 or 5.
e1+e2 is 3 or 4. e1 is 1 in Y ¹¹ , is an integer of 2 to 3 in Y ²¹ , and is 1 in Y ³¹ and Y ³² . e2 is 2 or 3 in Y ¹¹ or Y ²¹ , and 2 or 3 in Y ³¹ and Y ³² .
h1 is 1 in Y ¹¹ , is an integer of 2 or more (preferably 2) in Y ²¹ , and is 1 in Y ³¹ and Y ³² . h2 is an integer of 2 or more (preferably 2 or 3) in Y ¹¹ or Y ²¹ , and an integer of 1 or more (preferably 2 or 3) in Y ³¹ and Y ³² .
i1+i2 is 3 or 4 in Y ¹¹ , 4 in Y ¹² , and 3 or 4 in Y ³¹ and Y ³² . i1 is 1 in Y ¹¹ , 2 in Y ²¹ , and 1 in Y ³¹ and Y ³² . i2 is 2 or 3 in Y ¹¹ , 2 in Y ¹² , and 2 or 3 in Y ³¹ and Y ³² .
i3 is 2 or 3.
i4 is 2 or more in Y ¹¹ (preferably an integer of 2 to 10 and particularly preferably 2 to 6), and 1 or more in Y ³¹ and Y ³² (preferably an integer of 1 to 10). An integer of 6 is particularly preferable).
i5 is 2 or more, and preferably an integer of 2 to 7.

The carbon number of the alkylene group of Q ²² , Q ²³ , Q ²⁴ , Q ²⁵ , Q ²⁶ , Q ²⁷ , and Q ²⁸ is the same as that of compound (3-11), compound (3-21) and compound (3-31). It is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4 from the viewpoint of easy handling and further excellent abrasion resistance, light resistance and chemical resistance of the water/oil repellent layer. However, the lower limit of the number of carbon atoms of the alkylene group having a specific bond between carbon and carbon atoms is 2.

Examples of the ring structure for Z ¹ include the ring structures described above, and the preferred forms are also the same. Since A ¹ and Q ²⁴ are directly bonded to the ring structure in Z ¹ , for example, an alkylene group is not connected to the ring structure and A ¹ or Q ²⁴ is not connected to the alkylene group.
Z ^a is an (i5+1)-valent organopolysiloxane residue, and the following groups are preferable. However, R ^a in the following formula is an alkyl group (preferably having a carbon number of 1 to 10) or a phenyl group.

The number of carbon atoms of the alkyl group of R ^e1 , R ^e2 , R ^e3 or R ^e4 is 1 to 10 from the viewpoint of easy production of the compound (3-11), the compound (3-21) and the compound (3-31). Preferably, 1 to 6 is more preferable, 1 to 3 is further preferable, and 1 to 2 is particularly preferable.
The number of carbon atoms of the alkyl group portion of the acyloxy group of R ^e2 is preferably 1 to 10 from the viewpoint of easy production of the compound (3-11), the compound (3-21) and the compound (3-31). Is more preferable, 1 to 3 is further preferable, and 1 to 2 is particularly preferable.
h1 is easy to produce the compound (3-11), the compound (3-21) and the compound (3-31), and is further excellent in abrasion resistance and fingerprint stain removability of the water/oil repellent layer. 1-6 are preferable, 1-4 are more preferable, 1 or 2 is further preferable, and 1 is particularly preferable.
h2 is easy to produce the compound (3-11), the compound (3-21) and the compound (3-31), and further excellent in abrasion resistance and fingerprint stain removability of the water/oil repellent layer. 2-6 are preferred, 2-4 are more preferred, and 2 or 3 are particularly preferred.

Other forms of Y ¹¹ include a group (g3-1) (provided that d1+d3=1 (that is, d1 or d3 is 0), g1=d2×r1+d4×r1), and a group (g3-. 2) (provided that e1=1 and g1=e2×r1), a group (g3-3) (provided that g1=2×r1), a group (g3-4) (provided that h1=1) , G1=h2×r1), a group (g3-5) (where i1=1 and g1=i2×r1), a group (g3-6) (where g1=r1). A group (g3-7) (provided that g1=r1×(i3+1)), a group (g3-8) (provided that g1=r1×i4), a group (g3-9) (provided that g1=r1×i5).
Other forms of Y ²¹ include a group (g3-1) (where j2=d1+d3, d1+d3≧2, g2=d2×r1+d4×r1) and a group (g3-2) (where j2=e1). , E1=2, g2=e2×r1, e2=2), a group (g3-4) (provided that j2=h1, h1≧2, g2=h2×r1), and a group (g3- 5) (provided that j2=i1, i1 is 2 or 3, g2=i2×r1, and i1+i2 is 3 or 4).
Other forms of Y ³¹ and Y ³² include a group (g3-1) (provided that g3=d2×r1+d4×r1, k3=d2×r1+d4×r1) and a group (g3-2) (provided that: g3=e2×r1, k3=e2×r1), group (g3-3) (provided that g3=2×r1, k3=2×r1), group (g3-4) (provided that g3=h2×r1, k3=h2×r1), group (g3-5) (provided that g3=i2×r1, k3=i2×r1), group (g3-6) (provided that g3=r1, k3=r1), a group (g3-7) (where g3=r1×(i3+1), k3=r1×(i3+1)), a group (g3-8) (however, and g3=r1×i4 and k3=r1×i4) and the group (g3-9) (provided that g3=r1×i5 and k3=r1×i5).

(-A ¹ -) _e1 C(R ^e2 ) _4-e1-e2 (-Q ²² -G ¹ ) _e2 ...(g3-2)
-A ¹ -N(-Q ²³ -G ¹ ) ₂ ... (g3-3)
(-A ¹ -) _h1 Z ¹ (-Q ²⁴ -G ¹ ) _h2 ...(g3-4)
(-A ¹ -) _i1 Si(R ^e3 ) _4-i1-i2 (-Q ²⁵ -G ¹ ) _i2 ... (g3-5)
-A ¹ -Q ²⁶ -G ¹ ... (g3-6)
-A ¹ -CH(-Q ²² -G ¹ )-Si(R ^e3 ) _3-i3 (-Q ²⁵ -G ¹ ) _i3 ...(g3-7)
-A ¹ -[CH ₂ C(R ^e4 )(-Q ²⁷ -G ¹ )] _i4 -R ^e5 ... (g3-8)
-A ¹ -Z ^a (-Q ²⁸ -G ¹ ) _i5 ... (g3-9)

However, in the formulas (g3-1) to (g3-9), the A ¹ side is connected to (OX) _m , and the G ¹ side is connected to [—Si(R) _n L _3-n ].

G ¹ is a group (g3), and in each formula, when two or more G ¹ are present, two or more G ¹ may be the same or different. Codes other than G ¹ are the same as the codes in Expressions (g2-1) to (g2-9).
-Si(R ⁸ ) _3-r1 (-Q ³ -) _r1 ...(g3)
However, in the formula (g3), the Si side is connected to Q ²² , Q ²³ , Q ²⁴ , Q ²⁵ , Q ²⁶ , Q ²⁷ and Q ²⁸ , and the Q ³ side is [-Si(R) _n L _3-n ]. Connect to. R ⁸ is an alkyl group. Q ³ is an alkylene group, a group having —C(O)NR ⁶ —, —C(O)—, —NR ⁶ — or —O— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or —(OSi(R ⁹ ) ₂ ) _p —O—, and two or more Q ³ may be the same or different. r1 is 2 or 3. R ⁶ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁹ is an alkyl group, a phenyl group or an alkoxy group, and two R ⁹ may be the same or different. p is an integer of 0 to 5, and when p is 2 or more, (OSi(R ⁹ ) ₂ ) of 2 or more may be the same or different.

The number of carbon atoms of the alkylene group of Q ³ is such that compound (3-11), compound (3-21) and compound (3-31) can be easily produced, and the water- and oil-repellent layer has abrasion resistance, light resistance and From the viewpoint of further excellent chemical resistance, 1 to 10 is preferable, 1 to 6 is more preferable, and 1 to 4 is particularly preferable. However, the lower limit of the number of carbon atoms of the alkylene group having a specific bond between carbon and carbon atoms is 2.
The number of carbon atoms of the alkyl group of R ⁸ is preferably 1 to 10, more preferably 1 to 6, from the viewpoint of easy production of the compound (3-11), the compound (3-21) and the compound (3-31). 1-3 are more preferable, and 1-2 are particularly preferable.
The number of carbon atoms of the alkyl group of R ⁹ is preferably 1 to 10, more preferably 1 to 6, from the viewpoint of easy production of the compound (3-11), the compound (3-21) and the compound (3-31). 1-3 are more preferable, and 1-2 are particularly preferable.
The number of carbon atoms of the alkoxy group of R ⁹ is preferably 1 to 10 and more preferably 1 to 6 from the viewpoint of excellent storage stability of compound (3-11), compound (3-21) and compound (3-31). Preferably, 1-3 are more preferable, and 1-2 are particularly preferable.
p is preferably 0 or 1.

Examples of the compound (3-11), the compound (3-21) and the compound (3-31) include the compounds of the following formulas. The compound of the following formula is industrially easy to manufacture, easy to handle, and more excellent in water/oil repellency of the water/oil repellent layer, abrasion resistance, fingerprint stain removal property, lubricity, chemical resistance, light resistance and chemical resistance. It is preferable because it is excellent, and in particular, the light resistance is particularly excellent. R ^f in the compound of the following formula is the same as R ^f1 —(OX) _m —O— in formula (3-11) or R ^f2 —(OX) _m —O— in formula (3-21) above. The preferred embodiments are also the same. Q ^f in the compound of the following formula is the same as —(OX) _m —O— in the formula (3-31), and the preferred embodiments are also the same.

Examples of the compound (3-11) in which Y ¹¹ is the group (g2-1) include compounds of the following formulas.

Examples of the compound (3-11) in which Y ¹¹ is the group (g2-2) include the compounds of the following formulas.

Examples of the compound (3-21) in which Y ²¹ is the group (g2-2) include the compounds of the following formulas.

Examples of the compound (3-11) in which Y ¹¹ is the group (g2-3) include compounds of the following formulas.

Examples of the compound (3-11) in which Y ¹¹ is the group (g2-4) include the compounds of the following formulas.

Examples of the compound (3-11) in which Y ¹¹ is the group (g2-5) include the compounds of the following formulas.

Examples of the compound (3-11) in which Y ¹¹ is the group (g2-7) include compounds of the following formulas.

Examples of the compound (3-11) in which Y ¹¹ is the group (g3-1) include the compounds of the following formulas.

Examples of the compound (3-11) in which Y ¹¹ is the group (g3-2) include the compounds of the following formulas.

Examples of the compound (3-11) in which Y ¹¹ is the group (g3-3) include compounds of the following formulas.

Examples of the compound (3-11) in which Y ¹¹ is the group (g3-4) include the compounds of the following formulas.

Examples of the compound (3-11) in which Y ¹¹ is the group (g3-5) include compounds of the following formulas.

Examples of the compound (3-11) in which Y ¹¹ is the group (g3-6) include compounds of the following formulas.

Examples of the compound (3-11) in which Y ¹¹ is the group (g3-7) include the compounds of the following formulas.

Examples of the compound (3-21) in which Y ²¹ is the group (g2-1) include the compounds of the following formulas.

Examples of the compound (3-31) in which Y ³¹ and Y ³² are the group (g2-1) include the compounds of the following formulas.

Examples of the compound (3-31) in which Y ³¹ and Y ³² are the group (g2-2) include the compounds of the following formulas.

Examples of the compound (3-31) in which Y ³¹ and Y ³² are the group (g2-3) include the compounds of the following formulas.

Examples of the compound (3-31) in which Y ³¹ and Y ³² are the group (g2-4) include the compounds of the following formulas.

Examples of the compound (3-31) in which Y ³¹ and Y ³² are the group (g2-5) include the compounds of the following formulas.

Examples of the compound (3-31) in which Y ³¹ and Y ³² are the group (g2-6) include the compounds of the following formulas.

Examples of the compound (3-31) in which Y ³¹ and Y ³² are the group (g2-7) include the compounds of the following formulas.

Examples of the compound (3-31) in which Y ³¹ and Y ³² are the group (g3-2) include the compounds of the following formulas.

As the fluorine-containing ether compound, a compound represented by the formula (3X) is also preferable, because it is excellent in water repellency and oil repellency and abrasion resistance of the film.
[A-(OX) _m ] _j Z'[-Si(R) _n L _3-n ] _g ... (3X)

The compound (3X) is preferably a compound represented by the formula (3-1) from the viewpoint that the water/oil repellent layer is more excellent in water/oil repellency.
A-(OX) _m -Z ³¹ ...(3-1)
In formula (3-1), the definitions of A, X and m are the same as the definitions of each group in formula (3).

Z'is a (j+g)-valent linking group.
Z′ may be a group that does not impair the effects of the present invention, and examples thereof include an etheric oxygen atom or an alkylene group which may have a divalent organopolysiloxane residue, an oxygen atom, a carbon atom, and a nitrogen atom. , A silicon atom, a divalent to octavalent organopolysiloxane residue, and formula (3-1A), formula (3-1B), and formula (3-1A-1) to (3-1A-6) to Si( R) A group excluding _n L _3-n can be mentioned.

Z ³¹ is the group (3-1A) or the group (3-1B).
-Q ^a -X ³¹ (-Q ^b -Si(R) _n L _3-n ) _h (-R ³¹ ) _i ... (3-1A)
-Q ^c -[CH ₂ C(R ³² )(-Q ^d -Si(R) _n L _3-n )] _y -R ³³ ... (3-1B)

Q ^a is a single bond or a divalent linking group.
Examples of the divalent linking group include a divalent hydrocarbon group, a divalent heterocyclic group, —O—, —S—, —SO ₂ —, —N(R ^d )—, and —C(O). -, -Si(R ^a ) _2-, and groups formed by combining two or more of these. Here, R ^a is an alkyl group (preferably having a carbon number of 1 to 10) or a phenyl group. R ^d is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
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. The divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, and examples thereof include a phenylene group. The alkenylene group is preferably an alkenylene group having 2 to 20 carbon atoms, and the alkynylene group is preferably an alkynylene group having 2 to 20 carbon atoms.
Examples of the group formed by combining two or more of the above are, for example, —OC(O)—, —C(O)N(R ^d )—, an alkylene group having an etheric oxygen atom, and —OC(O)—. And an alkylene group having —, an alkylene group —Si(R ^a ) ₂ -phenylene group —Si(R ^a ) ₂ .

X ³¹ is a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom or a divalent to octavalent organopolysiloxane residue.
The alkylene group may have —O—, silphenylene skeleton group, divalent organopolysiloxane residue or dialkylsilylene group. The alkylene group may have a plurality of groups selected from the group consisting of —O—, silphenylene skeleton group, divalent organopolysiloxane residue and dialkylsilylene group.
The alkylene group represented by X ³¹ preferably has 1 to 20 carbon atoms, and particularly preferably has 1 to 10 carbon atoms.
Examples of the divalent to octavalent organopolysiloxane residue include a divalent organopolysiloxane residue and a (w+1)-valent organopolysiloxane residue described later.

Q ^b is a single bond or a divalent linking group.
The definition of the divalent linking group is the same as the definition described for Q ^a above.

R ³¹ is a hydroxyl group or an alkyl group.
The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1.

When X ³¹ is a single bond or an alkylene group, h is 1, i is 0,
When X ³¹ 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,
When X ³¹ is a carbon atom or a silicon atom, h is an integer of 1 to 3, i is an integer of 0 to 2, and h+i=3 is satisfied,
When X ³¹ is a divalent to octavalent 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.
If ^{_{_{(-Q b -Si (R) n}}} L 3-n) is two or more, two or more ^{_{_{(-Q b -Si (R) n}}} L 3-n) are be the same or different May be If R ³¹ is two or more, two or more ^{(-R 31)} may be be the same or different.

Q ^c 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 a compound.
The alkylene group which may have an etheric oxygen atom preferably has 1 to 10 carbon atoms, and particularly preferably has 2 to 6 carbon atoms.

R ³² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a hydrogen atom is preferable from the viewpoint of easy production of a compound.
A methyl group is preferred as the alkyl group.

Q ^d is a single bond or an alkylene group. The number of carbon atoms of the alkylene group is preferably 1-10, particularly preferably 1-6. From the viewpoint of easy production of the compound, Q ^d is preferably a single bond or —CH ₂ —.

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

y is an integer of 1 to 10, preferably an integer of 1 to 6.
Two or more [CH ₂ C(R ³² )(-Q ^d -Si(R) _n L _3-n )] may be the same or different.

As the group (3-1A), the groups (3-1A-1) to (3-1A-6) are preferable.
^{_{^{- (X 32) s1 -Q b1}}} -SiR n L 3-n ··· (3-1A-1)
^{_{^{^{- (X 33) s2 -Q a2}}}} -N [-Q b2 -Si (R) n3 L 3-n] 2 ··· (3-1A-2)
-Q ^a3 -G(R ^g )[-Q ^b3 -Si(R) _n L _3-n ] ₂ ... (3-1A-3)
^{_{^{_{- [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)
-Q ^a5- Si [-Q ^b5 _- Si(R) _n L _3-n ] ₃ ... (3-1A-5)
^{_{- [C (O) N (}} R d)] v -Q a6 -Z a '[-Q b6 -Si (R) n L 3-n] w ··· (3-1A-6)
The definitions of R, L, and n in formulas (3-1A-1) to (3-1A-6) are as described above.

X ³² is —O— or —C(O)N(R ^d )— (wherein N is bonded to Q ^b1 ).
The definition of R ^d is as described above.
s1 is 0 or 1.

Q ^b1 is an alkylene group. The alkylene group may have —O—, silphenylene skeleton group, divalent organopolysiloxane residue or dialkylsilylene group. The alkylene group may have a plurality of groups selected from the group consisting of —O—, silphenylene skeleton group, divalent organopolysiloxane residue and dialkylsilylene group.
When the alkylene group has —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group, it is preferable to have these groups between carbon atoms.

The alkylene group represented by Q ^b1 preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.

As Q ^b1 , when s1 is 0, —CH ₂ OCH ₂ CH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ CH ₂ Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ CH ₂ CH ₂ — are preferred. When (X ³² ) _s1 is —O—, —CH ₂ CH ₂ CH ₂ — and —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — are preferable. When (X ³² ) _s1 is —C(O)N(R ^d )—, an alkylene group having 2 to 6 carbon atoms is preferable (provided that N in the formula is bonded to Q ^b1 ). When Q ^b1 is these groups, the compound can be easily produced.

Specific examples of the group (3-1A-1) include the following groups. In the following formula, * represents a bonding position with (OX) _m .

X ³³ is —O—, —NH—, or —C(O)N(R ^d )—.
The definition of R ^d is as described above.

Q ^a2 is a single bond, an alkylene group, —C(O)—, or an etheric oxygen atom, —C(O)—, —C(O) between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms. ) A group having O—, —OC(O)— or —NH—.
The alkylene group represented by Q ^a2 preferably has 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
An etheric oxygen atom, —C(O)—, —C(O)O—, —OC(O)— or —NH between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ^a2. The number of carbon atoms of the group having-is preferably 2 to 10, and particularly preferably 2 to 6.

The Q ^a2, from the viewpoint of easily producing the _{_{_{_{compound, -CH 2 -, - CH 2}}}} CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 OCH 2 CH 2 -, - CH 2 NHCH 2 CH 2 -, -CH ₂ CH ₂ OC(O)CH ₂ CH ₂ -, -C(O)- are preferable (provided that the right side is bonded to N).

s2 is 0 or 1 (provided that it is 0 when Q ^a2 is a single bond). From the viewpoint of easy production of the compound, 0 is preferable.

Q ^b2 is an alkylene group or a group having a divalent organopolysiloxane residue, an etheric oxygen atom or —NH— between the carbon atoms of the alkylene group having 2 or more carbon atoms.
The alkylene group represented by Q ^b2 preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
The alkylene group having 2 or more carbon atoms represented by Q ^b2 has a divalent organopolysiloxane residue, an etheric oxygen atom or a group having —NH— between the carbon atoms and the carbon atom, and the carbon number is 2 to 10 Is preferable, and 2 to 6 is particularly preferable.

Q ^b2 is preferably —CH ₂ CH ₂ CH ₂ — or —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — from the viewpoint of easy production of the compound (provided that the right side is bonded to Si).

The two [-Q ^b2- Si(R) _n L _3-n ] may be the same or different.

Specific examples of the group (3-1A-2) include the following groups. In the following formula, * represents a bonding position with (OX) _m .

Q ^a3 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 a compound.
The alkylene group which may have an etheric oxygen atom preferably has 1 to 10 carbon atoms, and particularly preferably has 2 to 6 carbon atoms.

G is a carbon atom or a silicon atom.
R ^g is a hydroxyl group or an alkyl group. The alkyl group represented by R ^g preferably has 1 to 4 carbon atoms.
As G(R ^g ), C(OH) or Si(R ^ga )(wherein R ^ga is an alkyl group. From the viewpoint of easy production of a compound, the alkyl group preferably has 1 to 10 carbon atoms, and is methyl. Groups are particularly preferred).

Q ^b3 is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between the carbon atoms of the alkylene group having 2 or more carbon atoms.
The alkylene group represented by Q ^b3 preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
The carbon number of the alkylene group having 2 or more carbon atoms represented by Q ^b3 and having an etheric oxygen atom or a divalent organopolysiloxane residue between the carbon atoms is preferably 2 to 10 and more preferably 2 to 6 is particularly preferred.
The Q ^b3, from the viewpoint of easily producing the _{_{_{_{compound, -CH 2 CH 2 -, -}}}} CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 - is preferred.

The two [-Q ^b3 -Si(R) _n L _3-n ] may be the same or different.

Specific examples of the group (3-1A-3) include the following groups. In the following formula, * represents a bonding position with (OX) _m .

The definition of R ^d in formula (3-1A-4) is as described above.
s4 is 0 or 1.
Q ^a4 is a single bond or an alkylene group which may have an etheric oxygen atom.
The alkylene group which may have an etheric oxygen atom preferably has 1 to 10 carbon atoms, and particularly preferably has 2 to 6 carbon atoms.
t4 is 0 or 1 (provided that Q ^a4 is a single bond, it is 0).
As —Q ^a4 —(O) _t4 —, when s4 is 0, a single bond, —CH ₂ O—, —CH ₂ OCH ₂ —, or —CH ₂ OCH ₂ CH ₂ — is obtained from the viewpoint of easy production of the compound. O-, —CH ₂ OCH ₂ CH ₂ OCH ₂ — and —CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ — are preferable (provided that the left side is bonded to (OX) _m ) and s4 is 1. Is preferably a single bond, —CH ₂ — or —CH ₂ CH ₂ —.

Q ^b4 is an alkylene group, and the alkylene group is —O—, —C(O)N(R ^d )— (the definition of R ^d is as described above), a silphenylene skeleton group, a divalent group. It may have an organopolysiloxane residue or a dialkylsilylene group.
When the alkylene group has -O- or a silphenylene skeleton group, it is preferable to have a -O- or silphenylene skeleton group between carbon atoms. Further, when the alkylene group has —C(O)N(R ^d )—, a dialkylsilylene group or a divalent organopolysiloxane residue, the carbon atom-carbon atom or the terminal on the side bonded to (O) _u4 It is preferable to have these groups in
The alkylene group represented by Q ^b4 preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.

u4 is 0 or 1.
- _(O) u4 ^{-Q b4} - as it is from the viewpoint of easily producing the _{_{_{_{compound, -CH 2 CH 2 -, -}}}} CH 2 CH 2 CH 2 -, - CH 2 OCH 2 CH 2 CH 2 -, - CH 2 OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —, —OCH ₂ CH ₂ CH ₂ —, —OSi(CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ —, —OSi(CH ₃ ) ₂ OSi(CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ Si(CH ₃ ) ₂ PhSi(CH ₃ ) ₂ CH ₂ CH ₂ — are preferable (provided that the right side is bonded to Si).

Three _{^{[- (O) u4 -Q b4}} -Si (R) n L 3-n] may be be the same or different.

Specific examples of the group (3-1A-4) include the following groups. In the following formula, * represents a bonding position with (OX) _m .

Q ^a5 is an alkylene group which may have an etheric oxygen atom.
The alkylene group which may have an etheric oxygen atom preferably has 1 to 10 carbon atoms, and particularly preferably has 2 to 6 carbon atoms.
As Q ^a5 , from the viewpoint of easy production of a compound, —CH ₂ OCH ₂ CH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ — is preferable (however, the right side is bonded to Si).

Q ^b5 is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between the carbon atoms of the alkylene group having 2 or more carbon atoms.
The alkylene group represented by Q ^b5 preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
The carbon number of the alkylene group having 2 or more carbon atoms represented by Q ^b5, which has an etheric oxygen atom or a divalent organopolysiloxane residue between the carbon atoms, is preferably 2 to 10 and more preferably 2 to 6 is particularly preferred.
Q ^b5 is preferably —CH ₂ CH ₂ CH ₂ — or —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — from the viewpoint of easy production of the compound (provided that the right side is Si(R) _n L _3-n Combined with.).

The three [-Q ^b5 -Si(R) _n L _3-n ] may be the same or different.

Specific examples of the group (3-1A-5) include the following groups. In the following formula, * represents a bonding position with (OX) _m .

The definition of R ^d in formula (3-1A-6) is as described above.
v is 0 or 1.

Q ^a6 is an alkylene group which may have an etheric oxygen atom.
The alkylene group which may have an etheric oxygen atom preferably has 1 to 10 carbon atoms, and particularly preferably has 2 to 6 carbon atoms.
The Q ^a6, from the viewpoint of easily producing the _{_{_{_{compound, -CH 2 OCH 2 CH 2 CH}}}} 2 -, - CH 2 OCH 2 CH 2 OCH 2 CH 2 CH 2 -, - CH 2 CH 2 -, - CH 2 CH ₂ CH ₂ — is preferred (provided that the right side is bonded to Z ^{a ′} ).

Z ^{a ′} is a (w+1)-valent organopolysiloxane residue.
w is 2 or more, and preferably an integer of 2 to 7.
Examples of the (w+1)-valent organopolysiloxane residue include the same groups as the aforementioned (i5+1)-valent organopolysiloxane residue.

Q ^b6 is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between the carbon atoms of the alkylene group having 2 or more carbon atoms.
The alkylene group represented by Q ^b6 preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
The number of carbon atoms of the alkylene group having 2 or more carbon atoms represented by Q ^b6 and having an etheric oxygen atom or a divalent organopolysiloxane residue between the carbon atoms is preferably 2 to 10 and 2 to 6 is particularly preferred.
As Q ^b6 , —CH ₂ CH ₂ — and —CH ₂ CH ₂ CH ₂ — are preferable from the viewpoint of easy production of the compound.

The w [-Q ^b6 -Si(R) _n3 L _3-n ] may be the same or different.

The compound (3X) is also preferably the compound represented by the formula (3-2), because the water and oil repellent layer is more excellent in water and oil repellency.
[A-(OX) _m -Q ^a -] _j32 Z ³² [-Q ^b -Si(R) _n L _3-n ] _h32 (3-2)
In formula (3-2), the definitions of A, X, m, Q ^a , Q ^b , R, and L are the same as the definitions of each group in formula (3-1) and formula (3-1A). Is.

Z ³² is a (j32+h32)-valent hydrocarbon group or a (j32+h32)-valent hydrocarbon group having 2 or more carbon atoms and one or more ethereal oxygen atoms between the carbon atoms of the hydrocarbon group.
Z ³² is preferably a residue obtained by removing a hydroxyl group from a polyhydric alcohol having a primary hydroxyl group.
Z ³² is preferably a group represented by formula (Z-1) to formula (Z-5) from the viewpoint of easy availability of raw materials. However, R ³⁴ is an alkyl group, and preferably a methyl group or an ethyl group.

j32 is an integer of 2 or more, and is preferably an integer of 2 to 5 from the viewpoint that the water/oil repellent layer is more excellent in water/oil repellency. h32 is an integer of 1 or more, and the water/oil repellent layer has more abrasion resistance. From the viewpoint of superiority, an integer of 2 to 4 is preferable, and 2 or 3 is more preferable.

Specific examples of the fluorinated ether compound include those described in the following documents.
Perfluoropolyether-modified aminosilanes described in JP-A Nos. 11-029585 and 2000-327772.
A silicon-containing organic fluorine-containing polymer described in Japanese Patent No. 2874715.
Organosilicon compounds described in JP-A-2000-144097,
Fluorinated siloxane described in Japanese Patent Publication No. 2002-506887,
Organic silicone compounds described in Japanese Patent Publication No. 2008-534696,
A fluorinated modified hydrogen-containing polymer described in Japanese Patent No. 4138936;
Compounds described in U.S. Patent Application Publication No. 2010/0129672, International Publication No. 2014/126064, and JP-A-2014-070163,
Organosilicon compounds described in International Publication No. 2011/060047 and International Publication No. 2011/059430,
Fluorine-containing organosilane compounds described in WO 2012/064649,
A fluorooxyalkylene group-containing polymer described in JP 2012-72272 A,
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 Unexamined Patent 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 Fluorine-containing ethers described in WO/039226, WO2019/039341, WO2019/044479, WO2019/049753, WO20191633282 and JP2019-044158. Compound,
Perfluoro(poly)ether-containing silane compounds described in JP-A No. 2014-218639, International Publication No. 2017/022437, International Publication No. 2018/079743, and International Publication No. 2018/143433.
A perfluoro(poly)ether group-containing silane compound described in International Publication No. 2018/169002.
Fluoro (poly) ether group-containing silane compounds described in WO 2019/151442,
(Poly)ether group-containing silane compounds described in International Publication No. 2019/151445,
A compound containing a perfluoropolyether group described in WO 2019/098230,
Fluoropolyether group-containing polymer-modified silanes described in JP-A-2015-199906, JP-A-2016-204656, JP-A-2016-210854 and JP-A-2016-222859,
Fluorine-containing compounds described in WO2019/039083 and WO2019/049754.

Commercially available 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 Co., Ltd., manufactured by Daikin Industries, Ltd. Optool (registered trademark) DSX, Optool (registered trademark) AES, Optool (registered trademark) UF503, Optool (registered trademark) UD509, and the like.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
Examples 1 to 5 are examples, and Examples 6 to 7 are comparative examples.

[Evaluation]
(Coating film uniformity)
Under the condition of LED light irradiation, 100 sheets of 10 cm×10 cm glass substrate with water/oil repellent layer were visually inspected. Among the tested substrates, the ratio of the substrate without any defects is 90% or more out of the total number of sheets, "○", the ratio of the substrate without any defects is less than 90% among all the sheets. The case was designated as "x".
The defect means a defect region in which the water/oil repellent layer is not formed on the underlayer, a foreign substance observed in the water/oil repellent layer, and a foreign substance observed in the underlayer.

(Composition variation)
When manufacturing a base material with a base layer described later, 40 glass base materials were arranged in a vacuum vapor deposition apparatus to prepare 40 samples (base material with a base layer).
The composition of the underlayer in each of the 40 samples obtained was analyzed by X-ray photoelectron spectroscopy to determine the molar ratio of element I to silicon in each sample, and the maximum value of the above ratios of the 40 samples was determined. The difference between the minimum value and the minimum value was less than 0.3, and the difference was 0.3 or more was evaluated as "x".

[Synthesis of fluorinated compound]
Compound (3A) was obtained with reference to the method for producing compound (ii-2) described in WO 2014/126064.
Compound (3A): CF ₃ CF ₂ —OCF ₂ CF ₂ —(OCF ₂ CF ₂ CF ₂ CF ₂ OCF ₂ CF ₂ ) _n —OCF ₂ CF ₂ CF ₂ —C(O)NH—CH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃
The average value of the repeating unit number n: 13, the number average molecular weight of the compound (3A): 4,920.

(Example 1)
17.36 g of soda ash (manufactured by Soda Ash Japan) and 243.66 g of silica particles SC5500-SQ (trade name, manufactured by Admatechs) were added to Erich Rich Intensive Mixer EL-1 (manufactured by Japan Erich). The mixture was stirred and mixed at 2400 rpm for 30 seconds. The stirring speed was changed to 4800 rpm, 40.2 g of distilled water was added while stirring, and the mixture was further stirred at 4800 rpm for 60 seconds. Finally, the mixture was stirred at 1200 rpm for 60 seconds. The obtained particles were taken out of 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. The element contents of Si and Na in the sintered body 1 were measured by ICP emission spectroscopy (SPS5520 manufactured by Hitachi High-Tech Science Co., Ltd.), and the content of each element was converted into an oxide to obtain a mass% based on the total mass of these elements. .. The results are shown in Table 1.
Next, the sintered body 1 was allowed to stand in a thermo-hygrostat at 25° C. and a humidity of 50% for 7 days, and then the water content was measured. After performing the above-mentioned standing treatment, a separate drying treatment was not performed.
In a boat made of molybdenum in a vacuum vapor deposition apparatus (VTR-350M manufactured by ULVAC Kiko Co., Ltd.), 10 g of the sintered body 1 was used as a vapor deposition source for the underlayer, and a compound (3A was used as a fluorine-containing ether compound for a vapor deposition source of the water/oil repellent layer). ) Was placed in each case. A glass substrate (Dragontrail (registered trademark) manufactured by AGC Co., Ltd.) was placed in the vacuum vapor deposition apparatus, and the interior of the vacuum vapor deposition apparatus was evacuated to a pressure of 5×10 ⁻³ Pa or less.
The boat on which the granulated body 1 was placed was heated to 1,000° C. and vacuum-deposited on the glass base material to form a base layer having a thickness of 10 nm to obtain a glass base material with a base layer.
The boat on which the compound (3A) was placed was heated to 700° C., the condensate of the compound (3A) was vacuum-deposited on the underlayer to form a water/oil repellent layer having a thickness of 10 nm, and then heat treated at 140° C. for 30 minutes, A glass substrate with a water/oil repellent layer was obtained.

(Examples 2-7)
According to the same procedure as in Example 1 except that the raw materials used and the amount of water added were changed to the conditions shown in Table 1, and the stirring at 1200 rpm for 60 seconds in Example 1 was changed to the conditions shown in Table 1. A glass substrate with a water/oil repellent layer was obtained.

The "water addition amount" in Table 1 represents the mass ratio of water to be added to the mass of silica particles.
In the column of "mass ratio" in Table 1, particles having a particle size of less than 0.5 mm, particles having a particle size of 0.5 to 22.4 mm, and particle size of 22.4 mm are based on the total mass of all particles in the obtained vapor deposition material. Represents the respective content of super particles.
In the column "D90/D10" in Table 1, in the particle size distribution of the volume-based particles constituting the vapor deposition material, the particle diameter when the cumulative number of particles is 10% is D10, and the particle diameter when the cumulative number of particles is 90%. When defined as D90, it represents the ratio of D90 to D10 (D90/D10).
The "element I/silicon (molar ratio)" column in Table 1 represents the ratio of the total molar concentration of element I to the molar concentration of silicon in the vapor deposition material.
The “water content” column in Table 1 represents the water content of the vapor deposition material.

It was confirmed that the desired effects can be obtained with the vapor deposition material of the present invention.

The water- and oil-repellent layer-provided substrate of the present invention can be used in various applications where water- and oil-repellency is required. For example, display/input devices such as touch panels, transparent glass or transparent plastic members, lenses for glasses, antifouling members for kitchens, electronic devices, heat exchangers, water repellent and antifouling members such as batteries. It can be used as an antifouling member for toiletries, a member that requires liquid repellency while being conducted, a member for water repellency/waterproofing/sliding of a heat exchanger, a member for low surface friction such as a vibrating sieve and the inside of a cylinder. More specific examples of use include a front protective plate for a display, an antireflection plate, a polarizing plate, an antiglare plate, or those whose surface is subjected to an antireflection film treatment, a mobile phone (for example, a smartphone), a mobile information terminal. , A game console, a touch panel sheet of a device such as a remote controller, a touch panel display, various devices having a display input device for performing on-screen operations with a human finger or a palm (for example, glass or film used for a display unit, and Glass or film used for the exterior part other than the display part). In addition to the above, decorative building materials around water such as toilets, baths, washrooms, kitchens, wiring board waterproof members, heat exchanger water repellent/waterproof/sliding members, solar cell water repellent members, and printed wiring boards. Waterproof/water-repellent members, waterproof/water-repellent members for electronic device housings and electronic components, members for improving insulation of power lines, waterproof/water-repellent members for various filters, electromagnetic wave absorbers and sound absorbing materials. Such as waterproofing materials, baths, kitchen equipment, antifouling materials for toiletries, low-friction surface materials such as vibrating sieves and cylinders, mechanical parts, vacuum equipment parts, bearing parts, parts for transportation equipment such as automobiles, tools, etc. A surface protection member may be used.
In addition, the entire contents of the specification, claims, abstract and drawings of Japanese Patent Application No. 2018-242750 filed on Dec. 26, 2018 are cited herein, and the disclosure of the specification of the present invention is as follows. It is something to incorporate.

10 Base Material with Base Layer 12 Base Material 14 Base Layer 20 Base Material with Water and Oil Repellent Layer 22 Base Material 24 Base Layer 26 Water and Oil Repellent Layer

Claims

An oxide containing silicon and at least one element selected from the group consisting of a group 1 element, a group 2 element, a group 13 element, a group 15 element of the periodic table, and a transition metal element is included. Composed of particles,
A vapor deposition material in which the mass ratio of the particles having a particle size of 0.5 to 22.4 mm is 90% by mass or more based on the total mass of all particles.
In the volume-based particle size distribution of the particles constituting the vapor deposition material, 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, The vapor deposition material according to claim 1, wherein a ratio of D90 (D90/D10) is 6 or less.
The vapor deposition material according to claim 1 or 2, which has a water content of less than 2.0% by mass.
The vapor deposition material according to any one of claims 1 to 3, which is a sintered body or a molten body.
A substrate with an underlayer, wherein an underlayer containing an oxide containing the silicon and the element is formed on the substrate by vapor deposition using the vapor deposition material according to any one of claims 1 to 4. Production method.
An underlayer containing an oxide containing the silicon and the element is formed on a substrate by vapor deposition using the vapor deposition material according to any one of claims 1 to 4,
Next, a method for producing a substrate with a water/oil repellent layer, which comprises forming a water/oil repellent layer comprising a condensate of a fluorine-containing compound having a reactive silyl group on the underlayer.
The method for producing a substrate with a water/oil repellent layer according to claim 6, wherein the fluorine-containing compound is applied onto the underlayer by a dry coating method or a wet coating method and condensed.
The method for producing a substrate with a water/oil repellent layer according to claim 6 or 7, wherein the reactive silyl group is a group represented by the following formula (2).
-Si(R) n L 3-n ... (2)
However, R is a monovalent hydrocarbon group, L is a hydrolyzable group or a hydroxyl group, and n is an integer of 0 to 2.
The method for producing a substrate with a water/oil repellent layer according to any one of claims 6 to 8, wherein the fluorine-containing compound is a fluorine-containing compound having two or more reactive silyl groups.
The method for producing a substrate with a water/oil repellent layer according to any one of claims 6 to 9, wherein the fluorine-containing compound is a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a reactive silyl group. ..
The method for producing a substrate with a water/oil repellent layer according to claim 10, wherein the poly(oxyfluoroalkylene) chain is a poly(oxyfluoroalkylene) chain mainly containing an oxyperfluoroalkylene group.