JP2021172842A - Substrate with water and oil repellent layer, vapor deposition material, and manufacturing method of substrate with water and oil repellent layer - Google Patents

Abstract

To provide a substrate with a water and oil repellent layer excellent in wear resistance of the water and oil repellent layer; and to provide a vapor deposition material, and a manufacturing method of the substrate with the water and oil repellent layer.SOLUTION: In a substrate 10 with a water and oil repellent layer having a substrate 12, a ground layer 14, and a water and oil repellent layer 16 in this order, the water and oil repellent layer comprises a condensate of fluorine-containing compounds having a reactive silyl group, the ground layer contains an oxide containing silicon and a group 5 element in the periodic table, and the ratio of a molar concentration of the group 5 element in the ground layer to a molar concentration of silicon in the ground layer is 0.005-2.00.SELECTED DRAWING: Figure 1

Description

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

Contains poly (oxyperfluoroalkylene) chains and hydrolyzable silyl groups to impart water and oil repellency, fingerprint stain removal, lubricity (smoothness when touched by fingers), etc. to the surface of the substrate. It is known that a water- and oil-repellent layer made of a condensate of a fluorine-containing compound is formed on the surface of a base material by surface treatment using a fluorine compound.

Further, since the water- and oil-repellent layer is required to have abrasion resistance, a base layer is provided between them in order to improve the adhesiveness between the base material and the water- and oil-repellent layer. For example, Patent Documents 1 and 2 disclose that a silicon oxide layer is provided by vapor deposition between a base material and a water-repellent oil-repellent layer.

Japanese Unexamined Patent Publication No. 2014-218369 Japanese Unexamined Patent Publication No. 2012-722272

In recent years, the required performance for a water-repellent oil-repellent layer has become higher, and for example, a water-repellent oil-repellent layer having more excellent wear resistance is required.
When the present inventors evaluated a base material with a water-repellent oil-repellent layer having a base layer (silicon oxide layer) described in Patent Documents 1 and 2, there is room for improvement in the wear resistance of the water-repellent oil-repellent layer. Was found.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a base material with a water-repellent oil-repellent layer, a vapor-deposited material, and a base material with a water-repellent oil-repellent layer, which are excellent in abrasion resistance of the water-repellent oil-repellent layer.

As a result of diligent studies on the above problems, the present inventors have included an oxide containing silicon and Group 5 elements in the periodic table, and the sum of Group 5 elements in the base layer with respect to the molar concentration of silicon in the base layer. We have found that a base material with a water-repellent oil-repellent layer having excellent wear resistance of the water-repellent oil-repellent layer can be obtained by using a base layer having a molar concentration ratio within a predetermined range, and have reached the present invention.

That is, the inventors have found that the above problem can be solved by the following configuration.
[1] A base material with a water-repellent oil-repellent layer having a base material, a base layer, and a water-repellent oil-repellent layer in this order, and the water-repellent oil-repellent layer is a condensate of a fluorine-containing compound having a reactive silyl group. The base layer is composed of silicon and an oxide containing Group 5 elements of the periodic table, and the ratio of the total molar concentration of Group 5 elements in the base layer to the molar concentration of silicon in the base layer. Is a base material with a water-repellent and oil-repellent layer, which is 0.005 to 2.00.
[2] The base material with a water-repellent oil-repellent layer according to [1], wherein the Group 5 element is at least one element selected from the group consisting of vanadium, niobium and tantalum.
[3] The base material with a water-repellent oil-repellent layer according to [1] or [2], wherein the oxide further contains an alkali metal element.
[4] The ratio of the total molar concentration of the Group 5 elements of the periodic table to the molar concentration of silicon containing silicon and an oxide containing the Group 5 elements of the periodic table is 0.005 to 2.00. Vapor deposition material.
[5] The vapor deposition material of [4], wherein the Group 5 element is at least one element selected from the group consisting of vanadium, niobium and tantalum.
[6] The vapor-deposited material of [4] or [5], wherein the oxide further contains an alkali metal element.
[7] The oxide further contains at least one element I selected from the group consisting of nickel, iron, titanium, zirconium, molybdenum, and tungsten, and the sum of the elements I with respect to the molar concentration of silicon. The vapor-deposited material according to any one of [4] to [6], wherein the molar concentration ratio is 0.01 or less.
[8] The vapor-deposited material according to any one of [4] to [7], which is a molten material, a sintered body, or a granulated material.
[9] A method for producing a base material with a water-repellent oil-repellent layer having a base material, a base layer, and a water-repellent oil-repellent layer in this order, wherein any of the vapor deposition materials of [4] to [8] is used. By the vapor deposition method, the base material contains an oxide containing silicon and Group 5 elements of the periodic table, and the total molar amount of Group 5 elements in the base layer is relative to the molar concentration of silicon in the base layer. The base layer having a concentration ratio of 0.005 to 2.00 is formed, and then the water- and oil-repellent layer made of a condensate of a fluorine-containing compound having a reactive silyl group is formed on the base layer. A method for manufacturing a base material with a water- and oil-repellent layer.
[10] A method for producing a base material with a water-repellent oil-repellent layer having a base material, a base layer, and a water-repellent oil-repellent layer in this order, which comprises a compound containing silicon and a Group 5 element in the periodic table. By a wet coating method using a coating liquid containing a compound and a liquid medium, an oxide containing silicon and a Group 5 element of the periodic table is contained on the base material, and the molar concentration of silicon in the base layer. The base layer is formed in which the ratio of the total molar concentration of the Group 5 elements in the base layer to the base layer is 0.005-2.00, and then the base layer contains a reactive silyl group. A method for producing a base material with a water-repellent oil-repellent layer, which forms the water-repellent oil-repellent layer made of a condensate of a fluorine compound.

According to the present invention, it is possible to provide a base material with a water-repellent oil-repellent layer, a vapor-deposited material, and a base material with a water-repellent oil-repellent layer, which are excellent in abrasion resistance of the water-repellent oil-repellent layer.

It is sectional drawing which shows typically an example of the base material with a water-repellent oil-repellent layer of this invention.

In the present specification, the repeating unit represented by the formula 1 is referred to as a unit 1. Repeat units expressed by other formulas are also described in the same manner. The group represented by the formula 2 is referred to as the group 2. The groups represented by other formulas are also described in the same manner. The compound represented by the formula 3 is referred to as compound 3. Compounds represented by other formulas are also described in the same manner.
In the present specification, when "the alkylene group may have an A group", the alkylene group may have an A group between carbon atoms in the alkylene group, or the alkylene group-. It may have an A group at the end, such as A group.
In the present specification, the "aryl group" in the "aryloxy group" includes not only an aryl group but also a heteroaryl 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 1 to 10 carbon atoms) 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 “silphenylene skeleton group” is a group represented by −Si (R ^y ) ₂ PhSi (R ^y ) _2- (where Ph is a phenylene group and R ^y is a monovalent organic group). Is. As R ^y , an alkyl group (preferably 1 to 10 carbon atoms) is preferable.
A "dialkylsilylene group" is a group represented by −Si (R ^z ) _2- (where R ^z is an alkyl group (preferably having 1 to 10 carbon atoms)).
The "number average molecular weight" of a compound is calculated by determining the number (average value) of oxyfluoroalkylene groups with respect to the terminal groups by ¹ H-NMR and ^{19 F-NMR.}

Unless otherwise specified, the content of each element in the base layer is a value measured by depth direction analysis by X-ray photoelectron spectroscopy (XPS) using ion sputtering. The content of each element given by XPS analysis is molar concentration (mol%). Specifically, in the XPS analysis, the average molar concentration (mol%) in the underlying layer of each element was obtained from the depth direction profile of the vertical molar concentration (mol%) obtained by ion sputtering, and this value was calculated. The molar concentration (molar%) of each element. The measurement pitch of the profile in the depth direction is preferably 1 nm or less as a conversion depth calculated using the sputtering rate of a _{thermal oxide film (SiO 2 film) on a silicon wafer having a known film thickness.}
Unless otherwise specified, the content of each element in the vapor-deposited material is a value measured by wet analysis. The content of each element given by wet analysis is mass percent concentration (mass%). Atomic absorption method is used for measurement of alkali metal elements, inductively coupled plasma (ICP) emission spectroscopy or ICP mass analysis method is used for measurement of other elements, and calibration curve (matrix matching) method is used for quantification. The ratio of the molar concentration of each element can be obtained from the mass% of each element obtained by the wet analysis and the atomic weight (g / mol) of each element. The atomic weight used in the calculation is as follows.
Atomic weight of Si (g / mol): 28.09
Atomic weight of V (g / mol): 50.94
Atomic weight of Nb (g / mol): 92.91
Atomic weight of Ta (g / mol): 180.95
Atomic weight of Li (g / mol): 6.941
Atomic weight of Na (g / mol): 22.99
Atomic weight of K (g / mol): 39.10
Atomic weight of Rb (g / mol): 85.47
Atomic weight of Cs (g / mol): 132.9
Atomic weight of Ni (g / mol): 58.69
Atomic weight of Fe (g / mol): 55.85
Atomic weight of Ti (g / mol): 47.88
Atomic weight of Zr (g / mol): 91.22
Atomic weight of Mo (g / mol): 95.94
Atomic weight of W (g / mol): 183.8

The dimensional ratio in FIG. 1 is different from the actual one for convenience of explanation.

[Base material with water and oil repellent layer]
The base material with a water-repellent oil-repellent layer of the present invention is a base material with a water-repellent oil-repellent layer having a base material, a base layer, and a water-repellent oil-repellent layer in this order, and the water-repellent oil-repellent layer is a reactive silyl. It consists of a condensate of a fluorine-containing compound having a group.
Further, the base layer contains silicon and an oxide containing a Group 5 element in the periodic table, and the ratio of the total molar concentration of the Group 5 elements in the base layer to the molar concentration of silicon in the base layer is , 0.005-2.00.

The base material with a water-repellent oil-repellent layer of the present invention has excellent wear resistance of the water-repellent oil-repellent layer. The details of this reason have not been clarified, but it is presumed to be due to the following reasons.
Since Group 5 elements have empty p-orbitals and d-orbitals, it is considered that they are susceptible to lone electron pairs in oxygen and the like that can be possessed by the reactive silyl group of the fluorine-containing compound used for forming the water- and oil-repellent layer. .. It is presumed that this promoted the hydrolysis reaction and dehydration condensation reaction of the reactive silyl group of the fluorine-containing compound, and improved the wear resistance of the obtained water- and oil-repellent layer.

FIG. 1 is a cross-sectional view schematically showing an example of a base material with a water-repellent and oil-repellent layer of the present invention. The base material 10 with a water- and oil-repellent layer has a base material 12, a base layer 14 formed on one surface of the base material 12, and a water- and oil-repellent layer 16 formed on the surface of the base layer 14.
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 12 is not limited to this, and the base material with the water- and oil-repellent layer is not shown between the base material 12 and the base layer 14. It may have a layer of. Further, in the example of FIG. 1, the base layer 14 and the water-repellent oil-repellent layer 16 are in contact with each other. It may have a layer.
In the example of FIG. 1, the base layer 14 is formed on the entire surface of one surface of the base material 12, but the base layer 14 is not limited to this, and the base layer 14 is formed only in a part of the region of the base material 12. May be good. Further, in the example of FIG. 1, the water- and oil-repellent layer 16 is formed on the entire surface of the base layer 14, but the present invention is not limited to this, and the water- and oil-repellent layer 16 is formed only in a part of the base layer 14. It may be formed.
In the example of FIG. 1, the base layer 14 and the water-repellent oil-repellent layer 16 are formed only on one surface of the base material 12, but the present invention is not limited to this, and the base layer 14 and the water-repellent layer 16 are formed on both sides of the base material 12. The oil repellent layer 16 may be formed.

(Base material)
The base material is not particularly limited as long as it is a base material that is required to be provided with water and oil repellency. Specific examples of the material of the base material include metal, resin, glass, sapphire, ceramic, stone, and composite materials thereof. The glass may be chemically strengthened.
As the base material, a touch panel base material and a display base material are preferable, and a touch panel base material is particularly preferable. The base material for the touch panel preferably has translucency. “Having translucency” means that the vertically incident visible light transmittance according to JIS R3106: 1998 (ISO 9050: 1990) is 25% or more. As the material of the base material for the touch panel, glass or a transparent resin is preferable.
Further, examples of the base material include the following. Used for building materials, decorative building materials, interior goods, transportation equipment (for example, automobiles), signs / bulletin boards, drinkers / tableware, water tanks, ornamental equipment (forehead, boxes), laboratory equipment, furniture, art / sports / games Glass or resin, glass or resin used for exterior parts (excluding display parts) in devices such as mobile phones (for example, smartphones), mobile information terminals, game machines, and remote controls is also preferable. The shape of the base material may be plate-like or film-like.

The base material may be a base material having one surface or both sides subjected to surface treatment such as corona discharge treatment, plasma treatment, and plasma graft polymerization treatment. The surface-treated surface has better adhesion between the base material and the base layer, and as a result, the water- and oil-repellent layer has better wear resistance. Therefore, it is preferable to apply a surface treatment to the surface of the base material on the side in contact with the base layer.

(Underground layer)
The underlayer is a layer containing an oxide containing silicon and a Group 5 element of the periodic table.
Specific examples of Group 5 elements in the periodic table include vanadium, niobium, and tantalum, and vanadium is particularly preferable because the water- and oil-repellent layer has more excellent wear resistance. The Group 5 element may contain only one kind or two or more kinds.

The oxide contained in the base layer may be a mixture of oxides of the above elements (silicon and Group 5 elements) alone (for example, a mixture of silicon oxide and an oxide of Group 5 elements). , It may be a composite oxide containing two or more kinds of the above elements, or it may be a mixture of an oxide of the above element alone and a composite oxide.

The content of the oxide in the base layer is preferably 80% by mass or more, more preferably 95% by mass or more, and more preferably 100% by mass, because the water- and oil-repellent layer is more excellent in abrasion resistance with respect to the total mass of the base layer. Mass% (all of the underlying layer is an oxide) is particularly preferable.
The oxygen content in the base layer is preferably 40 to 70 mol% as the molar concentration (mol%) of oxygen atoms with respect to all the elements in the base layer, from the viewpoint of more excellent wear resistance of the water- and oil-repellent layer. 50-70 mol% is more preferable, and 60-70 mol% is particularly preferable. The oxygen content in the underlying layer is measured by depth direction analysis by XPS using ion sputtering.

The content of silicon in the underlayer is 16 to 99.6 mol because the water- and oil-repellent layer is more excellent in abrasion resistance as the molar concentration (mol%) of silicon with respect to all the elements except oxygen in the underlayer. % Is preferred, 30-99.4 mol% is more preferred, and 40-99.1 mol% is particularly preferred.
The content of silicon in the base layer is 10 to 99.6 from the viewpoint that the wear resistance of the water- and oil-repellent layer is more excellent as the mass percent concentration (mass%) of silicon with respect to all the elements except oxygen in the base layer. The mass% is preferable, 15 to 99.5 mass% is more preferable, and 20 to 99.2 mass% is particularly preferable.

The ratio of the total molar concentration of the Group 5 elements in the underlayer to the molar concentration of silicon in the underlayer is 0.005 to 2.00, and the water- and oil-repellent layer is more excellent in abrasion resistance. 0.01 to 1.00 is preferable, and 0.01 to 0.5 is particularly preferable.
The total content of Group 5 elements in the base layer is the total molar concentration (mol%) of Group 5 elements with respect to all elements except oxygen in the base layer, and the wear resistance of the water- and oil-repellent layer is more excellent. From the point of view, 0.5 to 67.7 mol% is preferable, 1.0 to 50.0 mol% is more preferable, and 10.0 to 33.3 mol% is particularly preferable.
The content of Group 5 elements in the base layer is the total mass percent concentration (mass%) of Group 5 elements with respect to all elements except oxygen in the base layer, and the wear resistance of the water- and oil-repellent layer is more excellent. Therefore, 1.6 to 86.9% by mass is preferable, 3.2 to 76.9% by mass is more preferable, and 3.2 to 62.4% by mass is particularly preferable.
The content of Group 5 elements means the content of one type of element when it contains one type of Group 5 element, and each element when it contains two or more types of Group 5 elements. Means the total content of.

The oxide contained in the base layer may further contain an alkali metal element because the water- and oil-repellent layer has more excellent wear resistance.
Specific examples of the alkali metal element include lithium, sodium, potassium, rubidium, and cesium. Sodium, potassium, and lithium are preferable, and sodium is particularly preferable, because the water- and oil-repellent layer has more excellent wear resistance. The alkali metal element may contain only one kind or two or more kinds.
The alkali metal element may exist as an oxide of one kind of alkali metal element alone, or exists as a composite oxide of one or more kinds of alkali metal elements and the above elements (silicon or Group 5 element). May be.
The ratio of the total molar concentration of the alkali metal elements in the base layer to the molar concentration of silicon in the base layer is preferably 0 to 1.0, preferably 0.001 from the viewpoint of better wear resistance of the water- and oil-repellent layer. ~ 0.5 is particularly preferable.
The content of the alkali metal element in the base layer is 0 because the water- and oil-repellent layer has better wear resistance as the total molar concentration (mol%) of the alkali metal element with respect to all the elements except oxygen in the base layer. ~ 30 mol% is preferable, 0 to 20 mol% is more preferable, and 0.1 to 15 mol% is particularly preferable.
The content of the alkali metal element in the base layer is 0 because the water- and oil-repellent layer has better wear resistance as the mass percent concentration (mass%) of the alkali metal element with respect to all the elements except oxygen in the base layer. ~ 40% by mass is preferable, 0 to 30% by mass is more preferable, and 0.1 to 20% by mass is particularly preferable.
The content of the alkali metal element means the content of one kind of element when it contains one kind of alkali metal element, and the content of each element when it contains two or more kinds of alkali metal elements. Means the sum of.

The underlying layer is also referred to as 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”). ) May be. As a specific example of the inhomogeneous layer, when a concentration gradient of components (horizontal or vertical direction of the surface formed by the layer) occurs in the layer (gradient structure), it is discontinuous in the components existing continuously. The case where other components are present (sea island structure) can be mentioned. Specifically, the concentration of compounds containing Group 5 elements (raw materials such as vanadium oxide, niobium oxide, and tantalum oxide) is the surface (the surface opposite to the base material) with respect to silicon oxide (silica). ), The silica matrix is dotted with high-concentration portions of the group 5 element-containing compound, and silica and the group 5 element compound form a checker pattern. Can be mentioned.
The base layer may be a single layer or a plurality of layers, but a single layer is preferable from the viewpoint of the process.
The base layer may have irregularities on its surface.

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

(Water and oil repellent layer)
The water- and 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 a group in which L of the group represented by the formula 2 described later is a hydrolyzable group.
The hydrolyzable silyl group becomes a silanol group represented by Si-OH by the hydrolysis reaction. The silanol groups further undergo 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 undergoing a dehydration condensation reaction with a silanol group derived from an oxide contained in the underlying layer. That is, the water- and oil-repellent layer contains a condensate in which some or all of the reactive silyl groups of the fluorine-containing compound have undergone a hydrolysis reaction and a dehydration condensation reaction.

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

<Fluorine-containing compound having a 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 and oil repellency of the water and oil repellent layer.

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

X is a fluoroalkylene group having one or more fluorine atoms.
The number of carbon atoms 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- and oil-repellent layer.
The fluoroalkylene group may be linear, branched or cyclic.
The fluoroalkylene group preferably has 1 or more fluorine atoms, and the water- and oil-repellent layer is more excellent in corrosion resistance. Therefore, 2 to 10 groups are preferable, and 2 to 4 groups are particularly preferable.
The fluoroalkylene group may be a group in which all hydrogen atoms in the fluoroalkylene group are substituted 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 -, - OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 -, - O-cycloC 4 F 6 -, - O-cycloC 5 F 8 -, - O -CycloC ₆ F _10- can be mentioned.
Here, -cycloC ₄ F _6- means a perfluorocyclobutane diyl group, and specific examples thereof include a perfluorocyclobutane-1,2-diyl group. -CycloC ₅ F ₈ - means a perfluoro cyclopentane-diyl group, and specific examples thereof include perfluoro cyclopentane-1,3-diyl group. -CycloC ₆ F _10- means a perfluorocyclohexanediyl group, and specific examples thereof include perfluorocyclohexane-1,4-diyl groups.

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

The poly (oxyfluoroalkylene) chain may contain only one type of (OX) or may contain two or more types of (OX).
The binding order of two or more types of (OX) is not limited, and may be randomly, alternately, or arranged in blocks.
Including two or more kinds of (OX) means that two or more kinds of (OX) having different carbon atoms are present in the fluorine-containing ether compound, and two or more kinds of (OX) having different hydrogen atom numbers are present. That, there are two or more types (OX) with different positions of hydrogen atoms, and even if the number of carbons is the same, the presence or absence of a side chain and the type of side chain (the number of side chains and the number of carbons in the side chain) Etc.) means that there are two or more types of (OX) that differ.
The arrangement of two or more (OX), for _{example, {(OCF 2) m21 ·} (OCF 2 CF 2) m22} structure represented by the, m21 amino (OCF ₂₎ and m22 amino (OCF ₂ CF ₂ ) and are randomly arranged. _Further, the structure represented by _{(OCF 2 CF 2 -OCF 2 CF} 2 CF 2 CF 2) m25 is a m25 amino _{(OCF 2} CF 2) and m25 amino _{(OCF 2 CF 2 CF 2 CF} 2) Indicates that they are arranged alternately.

_{As (OX) m} representing a poly (oxyfluoroalkylene) chain, [(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・ ( O-cycloC ₄ H _mg F _{(6- mg)} ) _m17 · (O-cycloC ₅ H _mh F _(8-mh) ) _m18 · (O-cycloC ₆ H _mi F _(10-mi) ) _m19 ] is preferable. Here, -cycloC ₄ H _mg F _{(6- mg)} represents a fluorocyclobutane diyl group, and a fluorocyclobutane-1,2-diyl group is preferable. -CycloC ₅ H _mh F _(8-mh) represents a fluorocyclopentane diyl group, preferably a fluorocyclopentane-1,3-diyl group. -CycloC ₆ H _mi F _(10-mi) represents a fluorocyclohexanediyl group, preferably a fluorocyclohexane-1,4-diyl group.
ma is 0 or 1, mb is an integer from 0 to 3, mc is an integer from 0 to 5, md is an integer from 0 to 7, me is an integer from 0 to 9, and mf is an integer from 0 to 9. It is an integer of 0 to 11, mg is an integer of 0 to 5, mh is an integer of 0 to 7, and mi is an integer of 0 to 9.
m11, m12, m13, m14, m15, m16, m17, m18 and m19 are each independently an integer of 0 or more, preferably 100 or less.
m11 + m12 + m13 + m14 + m15 + m16 + m17 + m18 + m19 are integers of 2 or more, preferably an integer of 2 to 200, more preferably an integer of 5 to 150, further preferably an integer of 5 to 100, and particularly preferably an integer of 10 to 50.
Among them, m12 is preferably an integer of 2 or more, and an integer of 2 to 200 is particularly preferable.
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. However, it may have a branched chain shape, and a linear shape is preferable from the viewpoint of more excellent wear resistance of the water-repellent oil-repellent layer.

In addition, m11 (OCH _ma F _(2-ma) ), m12 (OC ₂ H _mb F _(4-mb) ), m13 (OC ₃ H _mc F _(6-mc) ), m14 (OC ₄ H _md F _(8-md) ), m15 (OC ₅ H _me F _(10-me) ), m16 (OC ₆ H _mf F _(12-mf) ), m17 ( O-cycloC ₄ H _mg F _{(6- mg)} ), m18 (O-cycloC ₅ H _mh F _(8-mh) ), m19 (O-cycloC ₆ H _mi F _(10-mi) ) The joining order is not limited.
When m11 is 2 or more, a plurality of (OCH _ma F _(2-ma) ) may be the same or different.
When m12 is 2 or more, a plurality of (OC ₂ H _mb F _(4-mb) ) may be the same or different.
When m13 is 2 or more, a plurality of (OC ₃ H _mc F _(6-mc) ) may be the same or different.
When m14 is 2 or more, a plurality of (OC ₄ H _md F _(8-md) ) may be the same or different.
When m15 is 2 or more, a plurality of (OC ₅ H _me F _(10-me) ) may be the same or different.
When m16 is 2 or more, a plurality of (OC ₆ H _mf F _(12-mf) ) may be the same or different.
When m17 is 2 or more, a plurality of (O-cycloC ₄ H _mg F _{(6- mg)} ) may be the same or different.
When m18 is 2 or more, a plurality of (O-cycloC ₅ H _mh F _(8-mh) ) may be the same or different.
When m19 is 2 or more, a plurality of (O-cycloC ₆ H _mi F _(10-mi) ) may be the same or different.

(OX) _m preferably has the following structure.
_{{(OCF 2) m21 · (} OCF 2 CF 2) m22},
(OCF ₂ CF ₂ ) _m23 ,
(OCF ₂ CF ₂ CF ₂ ) _m24 ,
_{(OCF 2 CF 2 -OCF 2 CF} 2 CF 2 CF 2) m25,
{(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ ) _m26 · (OCF ₂ ) _m27 },
{(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ ) _m26 · (OCF ₂ CF ₂ ) _m27 },
{(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ ) _m26 · (OCF ₂ ) _m27 },
{(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ ) _m26 · (OCF ₂ CF ₂ ) _m27 },
_{(OCF 2 CF 2 CF 2 CF} 2 CF 2 -OCF 2) m28,
_{(OCF 2 CF 2 CF 2 CF} 2 CF 2 -OCF 2 CF 2) m28,
_{(OCF 2 CF 2 CF 2 CF} 2 CF 2 CF 2 -OCF 2) m28,
_{(OCF 2 CF 2 CF 2 CF} 2 CF 2 CF 2 -OCF 2 CF 2) m28,
_{(OCF 2 -OCF 2 CF 2 CF} 2 CF 2 CF 2) m28,
_{(OCF 2 -OCF 2 CF 2 CF} 2 CF 2 CF 2 CF 2) m28,
_{(OCF 2 CF 2 -OCF 2 CF} 2 CF 2 CF 2 CF 2) m28,
_{(OCF 2 CF 2 -OCF 2 CF} 2 CF 2 CF 2 CF 2 CF 2) m28.
However, m21 is an integer of 1 or more, m22 is an integer of 1 or more, m21 + m22 is an integer of 2 to 500, m23 and m24 are independently integers of 2 to 500, and m25 is an integer of 1. ~ 250 are integers, m26 and m27 are each independently greater than or equal to 1, m26 + m27 is an integer of 2 to 500, and m28 is an integer of 1 to 250.

(OX) _m is more preferably having the following structure from the viewpoint that a fluorine-containing ether compound can be easily produced.
_{{(OCF 2) m21 · (} OCF 2 CF 2) m22},
(OCF ₂ CF ₂ CF ₂ ) _m24 ,
_{(OCF 2 CF 2) 2 {} (OCF 2) m21 · (OCF 2 CF 2) m22-2},
_{(OCF 2 CF 2 -OCF 2 CF} 2 CF 2 CF 2) m25-1 OCF 2 CF 2,
_{(OCF 2 CF 2 CF 2 CF} 2 CF 2 -OCF 2) m28,
_{(OCF 2 CF 2 CF 2 CF} 2 CF 2 CF 2 -OCF 2) m28,
_{(OCF 2 CF 2 -OCF 2 CF} 2 CF 2 CF 2 CF 2) m28-1 OCF 2 CF 2,
_{(OCF 2 CF 2 -OCF 2 CF} 2 CF 2 CF 2 CF 2 CF 2) m28-1 OCF 2 CF 2.
However, for m22-2, m25-1 and m28-1, the number of m22, m25 and m28 is selected so as to be an integer of 1 or more.
Among these, from the viewpoint of abrasion resistance of the water- and oil-repellent layer is more excellent, _(OX) m _{is, {(OCF 2) m21 ·} (OCF 2 CF 2) m22} is preferably.
In _{{(OCF 2) m21 · (} OCF 2 CF 2) m22}, m22 / m21 from that abrasion resistance of the water- and oil-repellent layer and fingerprint stain removal properties more excellent, preferably 0.1 to 10, 0 .2 to 5.0 is more preferable, 0.2 to 2.0 is further preferable, 0.2 to 1.5 is particularly preferable, and 0.2 to 0.85 is most preferable.

The number average molecular weight of (OX) _m is preferably 1,000 to 20,000, more preferably 2,000 to 15,000, and particularly preferably 3,000 to 10,000.
When the number average molecular weight is at least the lower limit, the molecular chain of the fluorine-containing ether compound becomes long, so that the flexibility of the molecular chain of the fluorine-containing ether compound is improved. As a result, the reaction probability between the silanol group derived from the reactive silyl group of the fluorine-containing ether compound and the silanol group of the base layer is increased, so that the adhesiveness between the water-repellent oil-repellent layer and the base layer is further improved. As a result, the wear resistance of the water-repellent and oil-repellent layer is more excellent. Further, since the fluorine content of the water-repellent and oil-repellent layer is improved, the water- and oil-repellent properties are more excellent.
Further, when the number average molecular weight is not more than the upper limit value, the handleability at the time of film formation is more excellent.

The reactive silyl group is preferably a group represented by the formula 2.
−Si (R) _n L _3-n formula 2

R is a monovalent hydrocarbon group.
The monovalent hydrocarbon group is preferably a monovalent aliphatic hydrocarbon group (which may be saturated or unsaturated) or a monovalent aromatic hydrocarbon group, and is preferably a monovalent aliphatic hydrocarbon. Hydrogen groups are more preferred, and alkyl groups are particularly preferred.
The monovalent hydrocarbon group may be linear, branched or cyclic, and is preferably linear or branched. The monovalent hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.

L is a hydrolyzable group or a hydroxyl group.
The hydrolyzable group of L is a group that becomes a hydroxyl group by a hydrolyzing 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 a Si—O—Si bond. Further, the silanol group can form a Si—O—Si bond by undergoing a dehydration condensation reaction with a silanol group derived from an organic sulfur compound used for forming the underlying layer.

Specific examples of L, which is a 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. As the aryloxy group, an aryloxy group having 3 to 10 carbon atoms is preferable. As the halogen atom, a chlorine atom is preferable. 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 or a halogen atom having 1 to 4 carbon atoms is preferable from the viewpoint that the fluorine-containing ether compound can be more easily produced. As L, an alkoxy group having 1 to 4 carbon atoms is preferable and a long-term storage stability of the fluorine-containing ether compound is required because there is little outgassing during coating and the storage stability of the fluorine-containing ether compound is more excellent. The ethoxy group is particularly preferable, and the methoxy group is particularly preferable when the reaction time after coating is short.

n is an integer from 0 to 2.
n is preferably 0 or 1, and 0 is particularly preferable. The presence of a plurality of L makes the adhesion of the water-repellent oil-repellent layer to the underlying layer stronger.
When n is 0 or 1, the plurality of Ls present in one molecule may be the same or different. From the viewpoint of the availability of raw materials and the ease of producing a fluorine-containing ether compound, they are preferably the same. When n is 2, the plurality of Rs present in one molecule may be the same or different. From the viewpoint of the availability of raw materials and the ease of producing a fluorine-containing ether compound, they are preferably the same.

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

A is a perfluoroalkyl group or -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 of more excellent wear resistance of the film.
The perfluoroalkyl group may be linear or branched.
However, when A is −Q [−Si (R) _n L _3-n ] _k , j is 1.

Perfluoroalkyl groups 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 repellency of the film is more excellent.

Q is a linking group of (k + 1) valence. As will be described later, k is an integer of 1 to 10. Therefore, as Q, a linking group having a valence of 2 to 11 can be mentioned.
The Q may be a group that does not impair the effects of the present invention, for example, an alkylene group, a carbon atom, a nitrogen atom, or a silicon atom that may have an ethereal oxygen atom or a divalent organopolysiloxane residue. , 2-8 valent organopolysiloxane residues, and groups g2-1 to group g2-9 and groups g3-1 to group g3-9, which will be described later.

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

Z is a (j + g) valence linking group.
Z may be a group that does not impair the effects of the present invention, for example, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, which may have an ethereal oxygen atom or a divalent organopolysiloxane residue. Examples thereof include 2-8 valent organopolysiloxane residues, and groups g2-1 to group g2-9 and groups g3-1 to group g3-9.

j is an integer of 1 or more, and an integer of 1 to 5 is preferable from the viewpoint of more excellent water and oil repellency of the film, and 1 is particularly preferable from the viewpoint of easy production of compound 3.
g is an integer of 1 or more, and an integer of 2 to 4 is preferable, 2 or 3 is more preferable, and 3 is particularly preferable, from the viewpoint of more excellent wear resistance of the film.
k is an integer of 1 to 10, and an integer of 1 to 8 is preferable, and an integer of 2 to 6 is particularly preferable, from the viewpoint of more excellent wear resistance of the water- and oil-repellent layer.

As compound 3, compound 3-11, compound 3-21 and compound 3-31 are preferable from the viewpoint of being excellent in the initial water contact angle and abrasion resistance of the water-repellent and oil-repellent layer. Among these, Compound 3-11 and Compound 3-21 are particularly excellent in the initial water contact angle of the water-repellent oil-repellent layer, and Compound 3-31 is particularly excellent in the abrasion resistance of the water-repellent oil-repellent layer.

R ^f1- (OX) _m- O-Y ¹¹ [-Si (R) _n L _3-n ] _g1 formula 3-11
[R ^f2- (OX) _m- O-] _j2 Y ²¹ [-Si (R) _n L _3-n ] _g2 equation 3-21
[L _3-n (R) _n Si-] _k3 Y ^32- (OX) _m- O-Y ³¹ [-Si (R) _n L _3-n ] _g3 formula 3-31

In Equation 3-11, X, m, R, n and L are synonymous with the definitions of X, m, R, n and L in Equation 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 linking group having a (g1 + 1) valence, and a specific example thereof is the same as Z in the formula 3.
g1 is an integer of 1 or more, and an integer of 2 to 15 is more preferable, an integer of 2 to 4 is more preferable, and 2 or 3 is more preferable, and 3 is more preferable, because the water and oil repellent layer is more excellent in abrasion resistance. Especially preferable.

In Equation 3-21, X, m, R, n and L are synonymous with the definitions of X, m, R, n and L in Equation 3, respectively.
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 linking group having a (j2 + g2) valence, and a specific example thereof is the same as Z in the formula 3.
g2 is an integer of 1 or more, and is preferably an integer of 2 to 15, more preferably 2 to 6, further preferably 2 to 4, and particularly preferably 4 from the viewpoint of more excellent wear resistance of the water and oil repellent layer. ..

In Equation 3-31, X, m, R, n and L are synonymous with the definitions of X, m, R, n and L in Equation 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 linking group having a (k3 + 1) valence, and a specific example thereof is the same as Q in Equation 3.
Y ³¹ is a linking group having a (g3 + 1) valence, and a specific example thereof is the same as Z in the 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 ≧ 1), and a group g2-2 (where d1 or d3 is 0). , E1 = 1, g1 = e2, e2 ≧ 1), group g2-3 (where g1 = 2), group g2-4 (where h1 = 1, g1 = h2, h2 ≧ 1) ), Group g2-5 (where i1 = 1, g1 = i2, i2 ≧ 1), group g2-6 (where g1 = 1), group g2-7 (where, however, g1 = 1). g1 = i3 + 1), group g2-8 (where g1 = i4, i4 ≧ 1), or group g2-9 (where g1 = i5, i5 ≧ 1). May be good.
^{Y 21} in the formula 3-21 is a group g2-1 (where j2 = d1 + d3, d1 + d3 ≧ 2, g2 = d2 + d4, d2 + d4 ≧ 1), a group g2-2 (where j2 = e1, e1 = 2). , G2 = e2, e2 ≧ 1), group g2-4 (where j2 = h1, h1 ≧ 2, g2 = h2, h2 ≧ 1), or group g2-5 (where j2). = I1, i1 = 2, g2 = i2, i2 ≧ 1).
^{Further, Y 31} and Y ³² in the formula 3-31 are independently group g2-1 (where g3 = d2 + d4, k3 = d2 + d4) and group g2-2 (where g3 = e2, k3 = e2). ), Group g2-3 (where g3 = 2, k3 = 2), group g2-4 (where g3 = h2, k3 = h2), group g2-5 (where, however, g3 = h2). g3 = i2, k3 = i2), group g2-6 (where g3 = 1, k3 = 1), group g2-7 (where g3 = i3 + 1, k3 = i3 + 1), It may be a group g2-8 (where g3 = i4, k3 = i4) or a group g2-9 (where g3 = i5, k3 = i5).

^{_{(-A 1 -) e1 C (}} R e2) 4-e1-e2 (-Q 22 -) e2 formula g2-2
_{^{-A 1 -N (-Q 23 -)}} 2 Formula g2-3
(-A ^1- ) _h1 Z ¹ (-Q ^24- ) _h2 formula g2-4
^{_{(-A 1 -) i1 Si (}} R e3) 4-i1-i2 (-Q 25 -) i2 formula g2-5
−A ¹ −Q ²⁶ − Equation g2-6
^{-A 1 -CH (-Q 22 -)} - Si (R e3) 3-i3 (-Q 25 -) i3 formula g2-7
^{_{-A 1 - [CH 2 C (}} R e4) (- Q 27 -)] i4 -R e5 formula g2-8
^{-A 1 -Z a (-Q 28 -} ) i5 formula g2-9

However, in the formulas g2-1 to g2-9, A ¹ is connected to the (OX) _m side, and Q ²² , Q ²³ , Q ²⁴ , Q ²⁵ , Q ²⁶ , Q ²⁷ and Q ²⁸ are [-Si. (R) Connect to the _n L _{3-n] side.}

A ¹ is a single bond, an alkylene group, or an alkylene group having 2 or more carbon atoms having -C (O) NR ^6- , -C (O)-, -OC (O) O-,-between carbon atoms. A group having NHC (O) O-, -NHC (O) NR ^6- , -O-, -SO ₂ NR ^6- or -N (R ⁶ ) SO _2- , in which A ¹ is 2 in each equation. If there are more than ^one , two or more A1s may be the same or different. The hydrogen atom of the alkylene group may be substituted with a fluorine atom.
Q ¹¹ represents a single bond, -O-, alkylene group or a carbon of an alkylene group having 2 or more carbon atoms - -C between carbon atoms ^{(O) NR 6 -, -} C (O) -, - NR 6 - Alternatively, it is a group having −O−.
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 a 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) ^{A group having −, −NR 6−} or −O−, and ^{when two or more Q 22s} are present in each equation, the two or more Q ^22s may be the same or different.
Q ^23, the carbon of the alkylene group or an alkylene group having 2 or more carbon, - -C between carbon atoms ^{(O) NR 6 -, -} C (O) -, - NR 6 - or -O- a group having a There, the two of Q ²³ may be the same or different.
Q ^24, when atom in ^{Z 1 to Q 24} is attached is a carbon ^atom, a ^{Q 22,} when atoms in ^{Z 1 to Q 24} is attached is a nitrogen ^atom, a ^{Q 23,} in each ^{formula, Q 24} If is present 2 or more, two or more Q ²⁴ may be different even in the same.
Q ^25, the carbon of the alkylene group or an alkylene group having 2 or more carbon, - -C between carbon atoms ^{(O) NR 6 -, -} C (O) -, - NR 6 - or -O- a group having a Yes, if there are two or more ^{Q 25s in each equation, the two or more Q 25s} may be the same or different.
Q ^26, the carbon of the alkylene group or an alkylene group having 2 or more carbon, - -C between carbon atoms ^{(O) NR 6 -, -} C (O) -, - NR 6 - or -O- a group having a be.
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 represents an alkylene group, or a carbon atom of the alkylene group having 2 or more carbon atoms - a group having an organopolysiloxane residue of the ethereal oxygen atom or a divalent between carbon atoms.

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

R ^e1 is a hydrogen atom or an alkyl group, and when two or more ^{Re1s are present in each formula, two or more Re1s} may be the same or different.
^Re2 is a hydrogen atom, a hydroxyl group, an alkyl group or an acyloxy group.
^Re3 is an alkyl group.
^Re4 is a hydrogen atom or an alkyl group, and a hydrogen atom is preferable because it is easy to produce a compound. ^{When two or more Re 4s} are present in each equation, the two or more ^{Re 4s} may be the same or different.
^Re5 is a hydrogen atom or a halogen atom, and a hydrogen atom is preferable because it is easy to produce 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 21} , preferably 1 or 2, and 1 in Y ¹¹ , Y ³¹ and Y ³² .
d2 + d4 is ^{an integer of 1 to 5 in Y 11} or Y ²¹ , preferably 4 or 5, an integer of 1 to 5 in Y ³¹ and Y ³² , preferably an integer of 3 to 5 or 4 or. 5 is particularly preferable.
e1 + e2 is 3 or 4. ^e1, in ^{Y 11} is ^1, the ^{Y 21} is 2-3 ^integer, 1 in ^{Y 31} and ^{Y 32.} e2 is ^{1 to 3 in Y 11} or Y ²¹ , preferably 2 or 3, and is preferably ^{1 to 3 in Y 31} and Y ³² , preferably 2 or 3.
^h1, in ^{Y 11} is ^1, the ^{Y 21} is an integer of 2 or more (2 ^preferably), it is 1 in ^{Y 31} and ^{Y 32.} h2 is ^{an integer of 1 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 2 to 4 (preferably 3 or 4) in ^{Y 11 , 3 or 4 (preferably 4) in Y 12} , and an integer of 2 to 4 (3 or preferably) in Y ³¹ and Y ^32. 4 is preferable). ^i1, in ^{Y 11} is ^1, the ^{Y 21} is 2 or ^3, 1 in the ^{Y 31} and ^{Y 32. i2,} in ^{Y 11} is an integer from 1 to 3 (preferably 2 or ^3), in ^{Y 12} is 1 or 2 (2 is ^preferred), in the ^{Y 31} and ^{Y 32} integer from 1 to 3 ( 2 or 3 is preferable).
i3 is an integer of 0 to 3, preferably 1-3, and particularly preferably 2 or 3.
i4 is 1 or more (preferably an integer of 2 to 10 and particularly preferably an integer of 2 to 6) in ^{Y 11 and 1 or more (preferably an integer of 1 to 10) in Y 31} and Y ³² . An integer of 6 is particularly preferable).
i5 is ^{1 or more (preferably an integer of 2 to 7) in Y 11 and} 1 or more (preferably an integer of 2 to 7) in Y ³¹ and Y ³² .

The carbon number of the alkylene group of Q ²² , Q ²³ , Q ²⁴ , Q ²⁵ , Q ²⁶ , Q ²⁷ , and Q ²⁸ makes it easy to produce compound 3-11, compound 3-21, and compound 3-31, and repellent. From the viewpoint of further excellent wear resistance, light resistance and chemical resistance of the water-repellent layer, 1 to 10 are preferable, 1 to 6 are more preferable, and 1 to 4 are particularly preferable. However, when a specific bond is formed between carbon atoms, the lower limit of the number of carbon atoms of the alkylene group is 2.

Examples ^{of the ring structure in Z 1} include the above-mentioned ring structure, and the preferred form is 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 linked to the ring structure, and A ¹ and Q ²⁴ are not linked to the alkylene group.
Z ^a is a (i5 + 1) -valent organopolysiloxane residue, and the following groups are preferable. ^{However, Ra} in the following formula is an alkyl group (preferably 1 to 10 carbon atoms) or a phenyl group.

R ^{e1, R e2,} the number of carbon atoms in the alkyl group of ^{R e3} and ^{R e4} are compounds 3-11, from the viewpoint of easily preparing a compound 3-21 and compound 3-31, preferably 1-10, 1-6 More preferably, 1 to 3 is further preferable, and 1 to 2 is particularly preferable.
The number of carbon atoms in the alkyl group moiety of the acyloxy group R ^e2, the compounds 3-11, from the viewpoint of easily preparing a compound 3-21 and compound 3-31, 1-10, more preferably 1 to 6, 1 3 is more preferable, and 1 to 2 is particularly preferable.
h1 is preferably 1 to 6 because it is easy to produce compound 3-11, compound 3-21 and compound 3-31, and the water- and oil-repellent layer is more excellent in abrasion resistance and fingerprint stain removal property. 1 to 4 are more preferable, 1 or 2 is further preferable, and 1 is particularly preferable.
h2 is preferably 2 to 6 because it is easy to produce compound 3-11, compound 3-21 and compound 3-31, and the water- and oil-repellent layer is more excellent in abrasion resistance and fingerprint stain removal property. 2 to 4 are more preferable, and 2 or 3 is particularly preferable.

Other forms of Y ¹¹ include group g3-1 (where d1 + d3 = 1 (ie, d1 or d3 is 0), g1 = d2 × r1 + d4 × r1), group g3-2 (where d1 or d3 is 0). , E1 = 1, g1 = e2 × r1), group g3-3 (where g1 = 2 × r1), group g3-4 (where h1 = 1, g1 = h2 × r1). ), Group g3-5 (where i1 = 1, g1 = i2 × r1), group g3-6 (where g1 = r1), group g3-7 (where g1 = r1 ×) (I3 + 1)), group g3-8 (where g1 = r1 × i4), group g3-9 (where g1 = r1 × i5).
Other forms of Y ²¹ include group g3-1 (where j2 = d1 + d3, d1 + d3 ≧ 2, g2 = d2 × r1 + d4 × r1), group g3-2 (where j2 = e1, e1 = 2). , G2 = e2 × r1, e2 = 2), group g3-4 (where j2 = h1, h1 ≧ 2, g2 = h2 × r1), group g3-5 (where j2 = i1). , I1 is 2 or 3, g2 = i2 × r1, i1 + i2 is 3 or 4).
Other forms of Y ³¹ and Y ³² include the group g3-1 (where g3 = d2 × r1 + d4 × r1, k3 = d2 × r1 + d4 × r1), the group g3-2 (where g3 = e2 ×). r1, k3 = e2 × r1), group g3-3 (where g3 = 2 × r1, k3 = 2 × r1), group g3-4 (where g3 = h2 × r1, k3 = h2 × r1), group g3-5 (where g3 = i2 × r1, k3 = i2 × r1), group g3-6 (where g3 = r1, k3 = r1), Group g3-7 (where g3 = r1 × (i3 + 1), k3 = r1 × (i3 + 1)), group g3-8 (where g3 = r1 × i4, k3 = r1 × i4), The group g3-9 (where g3 = r1 × i5, k3 = r1 × i5) can be mentioned.

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

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

G ¹ is a group g3, in each formula, if G ¹ is present 2 or more, 2 or more G ¹ may be be the same or different. Code other than G ¹ is the same as the sign in the formula g2-1~ formula G2-9.
-Si (R ⁸ ) _3-r1 (-Q ^3- ) _r1 formula g3
However, in the formula g3, Si is connected to the Q ²² , Q ²³ , Q ²⁴ , Q ²⁵ , Q ²⁶ , Q ²⁷ and Q ²⁸ sides, and Q ³ is on the [-Si (R) _n L _3-n ] side. Connect to. R ⁸ is an alkyl group. Q ³ are carbon atoms in the alkylene group, having two or more alkylene groups having a carbon - -C between carbon atoms ^{(O) NR 6 -, -} C (O) -, - NR 6 - or a group having -O- or, _{^{- (OSi (R 9) 2}} ) is a p -O-, 2 or more ^{Q 3} are 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 the two R ^9s may be the same or different. p is an integer of 0 to 5, and when p is 2 or more, 2 or more (OSI (R ⁹ ) ₂ ) may be the same or different.

The alkylene group of Q ³ are compounds 3-11, that easily produce a compound 3-21 and compound 3-31, and excellent abrasion resistance of the water- and oil-repellent layer, light resistance and chemical resistance further From the point of view, 1 to 10 is preferable, 1 to 6 is more preferable, and 1 to 4 is particularly preferable. However, when a specific bond is formed between carbon atoms, the lower limit of the number of carbon atoms of the alkylene group is 2.
The ^{number of carbon atoms of the alkyl group of R 8} is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3 from the viewpoint that compound 3-11, compound 3-21 and compound 3-31 can be easily produced. , 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, and even more preferably 1 to 3 from the viewpoint that compound 3-11, compound 3-21 and compound 3-31 can be easily produced. , 1-2 are particularly preferable.
The ^{number of carbon atoms of the alkoxy group of R 9} is preferably 1 to 10, more preferably 1 to 6, and preferably 1 to 3 from the viewpoint of excellent storage stability of compound 3-11, compound 3-21 and compound 3-31. More preferably, 1 to 2 is 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 compounds of the following formulas are industrially easy to manufacture and handle, and the water and oil repellent layer has better water and oil repellency, abrasion resistance, fingerprint stain removal, lubricity, chemical resistance, light resistance and chemical resistance. It is preferable because it is excellent, and above all, the light resistance is particularly excellent. ^{R f} is under a compound of the formula, ^R f1 in formula 3-11 described above - ^R f2 in _(OX) m -O- or Formula 3-21 - is the same as _(OX) m -O-, also preferred embodiment The same is true. ^{The Q f} in the compound of the following formula is the same as that of − (OX) _m −O − in the formula 3-31, and the preferred embodiment is also the same.

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

Examples of the compound 3-11 in which Y ¹¹ is a group g2-2 include the compound of the following formula.

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 a group g2-3 include the compounds of the following formulas.

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

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

Examples of the compound 3-11 in which Y ¹¹ is a group g2-6 include the compounds of the following formulas.

Examples of the compound 3-11 in which Y ¹¹ is a group g2-7 include the compound of the following formula.

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 a group g3-2 include the compounds of the following formulas.

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

Examples of the compound 3-11 in which Y ¹¹ is a group g3-4 include the compound of the following formula.

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

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

Examples of the compound 3-11 in which Y ¹¹ is a group g3-7 include the compound of the following formula.

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 groups g2-3 include the compounds of the following formulas.

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

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

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

Specific examples of the fluorine-containing ether compound include those described in the following documents.
Perfluoropolyether-modified aminosilanes described in JP-A-11-029585 and JP-A-2000-327772,
Silicon-containing organic fluoropolymers described in Japanese Patent No. 2874715,
Organosilicon compounds described in JP-A-2000-144097,
Fluorinated siloxanes described in JP-A-2002-506887,
The organic silicone compound described in JP-A-2008-534696,
Fluorinated modified hydrogen-containing polymer according to Japanese Patent No. 4138936,
Compounds described in U.S. Patent Application Publication No. 2010/0129672, International Publication No. 2014/1260664 and JP2014-070163.
Organosilicon compounds according to WO 2011/060047 and WO 2011/059430,
Fluorine-containing organosilane compound according to International Publication No. 2012/064694,
Fluoroxyalkylene group-containing polymer described in JP2012-722272, International Publication No. 2013/042732, International Publication No. 2013/121984, International Publication No. 2013/121985, International Publication No. 2013/121986, International Publication No. Publication No. 2014/163004, Japanese Patent Application Laid-Open No. 2014-080473, International Publication No. 2015/0879902, International Publication No. 2017/038830, International Publication No. 2017/038832, International Publication No. 2017/187775, International Publication No. 2018/216630, International Publication No. 2019/039186, International Publication No. 2019/039226, International Publication No. 2019/039341, International Publication No. 2019/0444479, International Publication No. 2019/049753, International Publication No. 2019/ Fluorine-containing ether compounds described in No. 163282 and JP-A-2019-044158,
Perfluoro (poly) ether-containing silane compounds according to JP-A-2014-218369, International Publication No. 2017/022437, International Publication No. 2018/079743, International Publication No. 2018/143433,
Perfluoro (poly) ether group-containing silane compound according to International Publication No. 2018/169002,
Fluoro (poly) ether group-containing silane compound according to International Publication No. 2019/151442,
The (poly) ether group-containing silane compound described in WO 2019/151445, the perfluoropolyether group-containing compound 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 compound according to International Publication No. 2019/049754.

Commercially available products of fluorine-containing 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, and Daikin Industries, Ltd. Optool (registered trademark) DSX, Optool (registered trademark) AES, Optool (registered trademark) UF503, Optool (registered trademark) UD509 and the like.

[Manufacturing method of base material with water- and oil-repellent layer]
The base material with a water- and oil-repellent layer of the present invention preferably has a base layer obtained by a vapor deposition method or a wet coating method. Hereinafter, preferred embodiments of the method for producing a base material with a water- and oil-repellent layer of the present invention will be described for each embodiment.

(First Embodiment)
The first embodiment of the method for producing a base material with a water-repellent oil-repellent layer of the present invention is an embodiment in which a base layer is formed by a vapor deposition method.
Specifically, the first embodiment is a method for producing a base material having a water-repellent oil-repellent layer having a base material, a base layer, and a water-repellent oil-repellent layer in this order, wherein a vapor deposition material (described later) is used. According to the vapor deposition method used, an oxide containing silicon and a Group 5 element in the periodic table is contained on the base material, and the sum of the Group 5 elements in the base layer with respect to the molar concentration of silicon in the base layer. A fluorine-containing compound having a reactive silyl group on the base layer, which forms the base layer having a molar concentration ratio of 0.005 to 2.00 (hereinafter, also referred to as “fluorine-containing compound”. ), A method of forming the water-repellent and oil-repellent layer made of the condensate of) can be mentioned.
The base material, the base layer, and the water-repellent oil-repellent layer are as described in the above-mentioned base material with the water-repellent oil-repellent layer of the present invention, and thus the description thereof will be omitted.

A specific example of the vapor deposition method using a vapor deposition material is a vacuum vapor deposition method. The vacuum vapor deposition method is a method in which a vaporized material is evaporated in a vacuum chamber and adhered to the surface of a base material.
The temperature at the time of vapor deposition (for example, when a vacuum vapor deposition apparatus is used, the temperature of the boat on which the vapor deposition material is installed) is preferably 100 to 3000 ° C, particularly preferably 500 to 3000 ° C.
The pressure during vapor deposition (for example, when a vacuum vapor deposition apparatus is used, the pressure in the tank in which the vapor deposition material is installed) is preferably 1 Pa or less, and particularly preferably 0.1 Pa or less.
When the underlayer is formed by using the 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 vaporized material include a resistance heating method in which the vaporized material is melted and evaporated on a refractory metal resistance heating boat, an electron beam is irradiated to the vaporized material, and the vaporized material is directly heated to surface. There is an electron gun method that melts and evaporates. As a method of evaporating the vaporized material, since it can be heated locally, the refractory substance can also be vaporized, and since the temperature is low where the electron beam does not hit, there is no risk of reaction with the container or contamination of impurities. The gun method is preferred.
As a method of evaporating the vaporized material, a plurality of boats may be used, or all the vaporized materials may be put in a single boat and used. The vapor deposition method may be co-deposited or alternate vapor deposition or the like. Specifically, in an example in which silica and a Group 5 element source (vanadium oxide, niobium oxide, tantalum oxide, etc.) are mixed and used in the same boat, silica and the above Group 5 element source are placed in separate boats. Examples include co-depositing, and similarly, examples of alternating vapor deposition in separate boats can be mentioned. The conditions and order of vapor deposition are appropriately selected depending on the composition of the underlying layer.

The water- and oil-repellent layer can be formed by any production method of dry coating and wet coating using a fluorine-containing compound or a composition containing a fluorine-containing compound and a liquid medium (hereinafter, also referred to as “composition”).
Specific examples of the liquid medium contained in the composition include water and an organic solvent. 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, for example, C ₆ F ₁₃ H (AC-2000: product name, manufactured by AGC Inc.), C ₆ F ₁₃ C ₂ H ₅ (AC-6000: product name). , AGC), C ₂ F ₅ CHFCHFCF ₃ (Bertrel: 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, for example, 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, C ₄ F ₉ OC ₂ H ₅ (Novec-7200: Product name, manufactured by 3M), 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 the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

As the non-fluorine-based organic solvent, a compound consisting only of a hydrogen atom and a carbon atom and a compound consisting only of a hydrogen atom, a carbon atom and an oxygen atom are preferable, and specifically, a hydrocarbon-based organic solvent and a ketone-based organic solvent are used. , Ether-based organic solvent, ester-based organic solvent, alcohol-based organic solvent can be mentioned.
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-based 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% by mass, particularly preferably 1 to 30% by mass, based on the total mass of the composition.
The content of the liquid medium in the composition is preferably 50 to 99.99% by mass, particularly preferably 70 to 99% by mass, based on the total mass of the composition.

The water-repellent and oil-repellent layer can be produced, for example, by the following method.
-A method of treating the surface of the base layer by a dry coating method using a fluorine-containing compound or a composition to form a water-repellent oil-repellent layer on the surface of the base layer.
-A method in which a composition is applied to the surface of a base layer by a wet coating method and dried to form a water-repellent and oil-repellent layer on the surface of the base layer.

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

Specific examples of the wet coating method include spin coating method, wipe coating method, spray coating method, squeegee coating method, dip coating method, die coating method, inkjet method, flow coating method, roll coating method, casting method, Langmuir Brodget. The method and the gravure coat method can be mentioned.

The drying temperature after the composition is wet-coated is preferably 20 to 200 ° C, particularly preferably 80 to 160 ° C.

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

<Embedded material>
The vapor deposition material of the present invention contains silicon and an oxide containing Group 5 elements in the periodic table, and the ratio of the total molar concentration of Group 5 elements to the molar concentration of silicon is 0.005 to 2.00. ..
In the present invention, the vapor deposition material means a material used for vapor deposition. The vapor-deposited material of the present invention is suitably used for forming a base layer in the above-mentioned base material with a water-repellent and oil-repellent layer.

Since the preferred embodiment of the Group 5 element contained in the vapor deposition material is the same as that of the base layer, the description thereof will be omitted.
When the vapor-deposited material contains niobium or tantalum, there is an advantage that the content of niobium and tantalum in the underlying layer can be easily adjusted as compared with the case where the vapor-deposited material contains Group 5 elements other than niobium and tantalum.

The oxide contained in the vapor deposition material may be a mixture of oxides of the above elements (silicon and Group 5 elements) alone (for example, a mixture of silicon oxide and an oxide of Group 5 elements). , It may be a composite oxide containing two or more kinds of the above elements, or it may be a mixture of an oxide of the above element alone and a composite oxide.

The content of the oxide in the thin-film vapor deposition material is preferably 80% by mass or more, more preferably 95% by mass or more, and more preferably 100% by mass, from the viewpoint that the wear resistance of the water-repellent oil-repellent layer is more excellent with respect to the total mass of the thin-film deposition material. Mass% (all of the vapor deposition material is an oxide) is particularly preferable.
The oxygen content in the vapor deposition material is preferably 40 to 70 mol% as the molar concentration (mol%) of oxygen atoms with respect to all the elements in the vapor deposition material, from the viewpoint of more excellent wear resistance of the water- and oil-repellent layer. 50-70 mol% is more preferable, and 60-70 mol% is particularly preferable. The oxygen content in the vapor-deposited material is measured by XPS analysis or the like for the vapor-deposited material that has been sufficiently pulverized and pelletized.

The content of silicon in the vapor deposition material is 14 to 99 mol% as the molar concentration (mol%) of silicon with respect to all elements except oxygen in the vapor deposition material, from the viewpoint of better wear resistance of the water-repellent oil-repellent layer. Preferably, 22-97 mol% is more preferable, and 30-94 mol% is particularly preferable.
The content of silicon in the vapor deposition material is 10 to 99 mass% from the viewpoint that the wear resistance of the water-repellent oil-repellent layer is more excellent as the mass percent concentration (mass%) of silicon with respect to all the elements except oxygen in the vapor deposition material. Is preferable, 15 to 97% by mass is more preferable, and 20 to 95% by mass is particularly preferable.

The ratio of the total molar concentration of the Group 5 elements in the vapor deposition material to the molar concentration of silicon in the vapor deposition material is 0.005 to 2, and the wear resistance of the water- and oil-repellent layer is more excellent. 01 to 1.00 is preferable, and 0.01 to 0.5 is particularly preferable.
The total content of Group 5 elements in the vapor deposition material is the total molar concentration (mol%) of Group 5 elements with respect to all elements except oxygen in the vapor deposition material, and the wear resistance of the water and oil repellent layer is more excellent. From the point of view, 0.5 to 67.7 mol% is preferable, 1.0 to 50.0% mol% is more preferable, and 10.0 to 33.3 mol% is particularly preferable.
The total content of Group 5 elements in the vapor deposition material is the total mass percent concentration (mass%) of Group 5 elements with respect to all elements in the underlying layer except oxygen in the vapor deposition material, and is the resistance of the water and oil repellent layer. From the viewpoint of more excellent wear resistance, 1.6 to 86.9% by mass is preferable, 3.2 to 76.9% by mass is more preferable, and 3.2 to 62.4% by mass is particularly preferable.

The oxide contained in the vapor-deposited material may further contain an alkali metal element because the water- and oil-repellent layer has more excellent wear resistance. Since the preferred embodiment of the alkali metal element is the same as that of the base layer, the description thereof will be omitted.
The alkali metal element may exist as an oxide of one kind of alkali metal element alone, or exists as a composite oxide of one or more kinds of alkali metal elements and the above elements (silicon or Group 5 element). May be.
The ratio of the total molar concentration of the alkali metal elements of the vapor deposition material to the molar concentration of silicon of the vapor deposition material is preferably 0 to 1.0, preferably 0.001 to 0, from the viewpoint of better wear resistance of the water and oil repellent layer. .5 is particularly preferable.
The content of the alkali metal element in the vapor deposition material is 0 because the abrasion resistance of the water- and oil-repellent layer is more excellent as the total molar concentration (mol%) of the alkali metal element with respect to all the elements except oxygen in the vapor deposition material. ~ 30 mol% is preferable, 0 to 20 mol% is more preferable, and 0.1 to 15 mol% is particularly preferable.
The content of the alkali metal element in the vapor deposition material is 0 because the abrasion resistance of the water- and oil-repellent layer is more excellent as the mass percent concentration (mass%) of the alkali metal element with respect to all the elements except oxygen in the vapor deposition material. ~ 40% by mass is preferable, 0 to 30% by mass is more preferable, and 0.1 to 20% by mass is particularly preferable.

The oxide contained in the vapor deposition material is at least one element I selected from the group consisting of nickel, iron, titanium, zirconium, molybdenum, and tungsten as long as it is not contained in the underlying layer obtained by vapor deposition. May include.
Element I may exist as an oxide of one kind of element alone, or may exist as a composite oxide of one or more kinds of element I and the above-mentioned element (silicon or Group 5 element). ..
The ratio of the total molar concentration of the element I of the vapor-deposited material to the molar concentration of silicon of the vapor-deposited material is preferably 0 to 0.01, preferably 0 to 0.001, from the viewpoint of better wear resistance of the water- and oil-repellent layer. Especially preferable.
The content of the element I in the vapor deposition material is preferably 1 mol% or less, preferably 0.1 mol% or less, as the total molar concentration (mol%) of the element I with respect to all the elements in the vapor deposition material except oxygen in the vapor deposition material. Is particularly preferable. If the content of the element I in the vapor deposition material is 1 mol% or less, the element I obtained by the vapor deposition is unlikely to be contained in the base layer, or even if it is contained in the base layer, the amount is small, so that it is water repellent. There is little effect on the performance of the oil layer and the base layer.
The content of element I means the content of one kind of element when it contains one kind of element I, and means the total content of each element when it contains two or more kinds of element I. ..

Specific examples of the form of the vapor deposition material include powder, molten material, sintered body, granulated material, and crushed material, and from the viewpoint of handleability, the molten material, sintered body, and granulated material are preferable.
Here, the molten material means a solid material obtained by melting the powder of the vapor-deposited material at a high temperature and then cooling and solidifying it. The sintered body means a solid material obtained by firing the powder of the vapor-deposited material, and if necessary, instead of the powder of the vapor-filmed material, the powder is press-formed and the molded body is used. May be good. The granulated material means a solid substance obtained by kneading a powder of a vapor deposition material and a liquid medium (for example, water or an organic solvent) to obtain particles, and then drying the particles.

The vapor deposition material can be produced, for example, by the following method.
-A method of obtaining a powder of a vapor-deposited material by mixing a powder of silicon oxide and a powder of an oxide of a Group 5 element.
-A method of obtaining granules of a vapor-deposited material by kneading the powder and water of the vapor-deposited material to obtain particles and then drying the particles.
-A powder containing silicon (for example, a powder composed of silicon oxide, silica sand, silica gel) and a powder containing a Group 5 element (for example, a powder containing an oxide of a Group 5 element, a carbonate, a sulfate, etc.) A method of obtaining a sintered body by drying a mixture of nitrate, oxalate, hydroxide) and water, and then firing the dried mixture or a molded product obtained by press-molding the dried mixture.
-Powder containing silicon (for example, powder composed of silicon oxide, silica sand, silica gel) and powder containing Group 5 element (for example, powder of oxide of Group 5 element, carbonate, sulfate, etc. A method in which a melt is obtained by melting the nitrate (nitrate, oxalate, hydroxide) at a high temperature and then cooling and solidifying the melt.

(Second Embodiment)
The second embodiment of the method for producing a base material with a water- and oil-repellent layer of the present invention is an embodiment in which the base layer is formed by a wet coating method.
Specifically, a second embodiment is a method for producing a base material having a water-repellent oil-repellent layer having a base material, a base layer, and a water-repellent oil-repellent layer in this order, wherein a compound containing silicon and a compound are used. By a wet coating method using a coating liquid containing a compound containing a Group 5 element in the periodic table and a liquid medium, an oxide containing silicon and a Group 5 element is contained on the base material, and the base layer is formed. The underlayer is formed in which the ratio of the total molar concentration of the Group 5 elements in the underlayer to the molar concentration of silicon in the underlayer is 0.005 to 2.00, and then the reaction is carried out on the underlayer. Examples thereof include a method of forming the water-repellent oil-repellent layer made of a condensate of a fluorine-containing compound having a silyl group.
The base material, the base layer, and the water-repellent oil-repellent layer are as described in the above-mentioned base material with the water-repellent oil-repellent layer of the present invention, and thus the description thereof will be omitted.

A specific example of the wet coating method for forming the base layer is the same as the case where the water-repellent oil-repellent layer is formed by the wet coating method in the first embodiment, and thus the description thereof will be omitted.
It is preferable that the coating film is wet-coated and then the coating film is dried. The drying temperature of the coating film is preferably 20 to 200 ° C, particularly preferably 80 to 160 ° C.

Since the method for forming the water-repellent oil-repellent layer in the second embodiment is the same as the method for forming the water-repellent oil-repellent layer in the first embodiment, the description thereof will be omitted.
Further, also in the second embodiment, the operation for improving the abrasion resistance of the water-repellent oil-repellent layer described in the first embodiment may be carried out.

<Coating liquid used to form the base layer>
The coating liquid used for forming the base layer contains a compound containing silicon, a compound containing a Group 5 element, and a liquid medium.

Specific examples of the silicon compound include a partial condensate of silicon oxide, silicic acid and silicic acid, and a partially hydrolyzed condensate of alkoxysilane and alkoxysilane.
The content of the silicon compound may be appropriately set so that the content of silicon in the underlying layer is within the above range.

Specific examples of compounds containing Group 5 elements include oxides of Group 5 elements, alkoxides of Group 5 elements, carbonates of Group 5 elements, sulfates of Group 5 elements, and nitrates of Group 5 elements. , Group 5 element oxalate and Group 5 element hydroxide.
The content of the compound containing the Group 5 element may be appropriately set so that the ratio of the total molar concentration of the Group 5 element to the molar concentration of silicon in the underlying layer is within the above range.

The coating liquid may further contain a compound containing an alkali metal element.
Compounds containing alkali metal elements include alkali metal element oxides, alkali metal element alkoxides, alkali metal element carbonates, alkali metal element sulfates, alkali metal element nitrates, alkali metal element oxalates, and alkalis. Examples include hydroxides of metal elements.
The content of the compound containing the alkali metal element may be appropriately set so that the ratio of the total molar concentration of the alkali metal element to the molar concentration of silicon in the underlying layer is within the above range.

Specific examples of the liquid medium contained in the coating liquid are the same as those of the liquid medium described in the formation of the water-repellent oil-repellent layer in the first embodiment, and thus the description thereof will be omitted.
The content of the liquid medium is preferably 0.01 to 20% by mass, particularly preferably 0.1 to 10% by mass, based on the total mass of the coating liquid used for forming the underlying layer.

Hereinafter, the present invention will be described in detail with reference to examples. Examples 1 to 17 are examples, and examples 18 to 20 are comparative examples. However, the present invention is not limited to these examples. The blending amount of each component in the table described later indicates a mass standard.
[Physical characteristics and evaluation]
(Content of each element in the base layer)
C ₆₀ X-ray photoelectron spectroscopy using an ion sputtering by (XPS), was obtained in the depth direction profile of the molar concentration of each element (mol%). Here, the molar concentration (molar%) of fluorine derived from the water-repellent oil-repellent layer with respect to all the elements detected by XPS analysis is that of fluorine, considering from the surface side of the depth direction profile of the base material with the water-repellent oil-repellent layer. The starting point A was defined as the point where the molar concentration was 10 mol% or less. Further, the end point B is the point where the molar concentration (mol%) of any element existing only in the base material with respect to all the elements detected by XPS analysis exceeds 30% of the molar concentration (molar%) in the base material for the first time. And said. The starting point A to the ending point B were defined as the base layer, and the ratio of the average value of the molar concentration (mol%) of the target element to the average value of the molar concentration (mol%) of silicon in the base layer was calculated. Incidentally, when obtaining the depth profile of the group 5 element and the alkali metal elements of the periodic table in the underlying layer by XPS, it is preferable to use a C ₆₀ ion sputtering. Moreover, aluminum was selected as an arbitrary element existing only in the base material. When the base layer does not contain aluminum and the base material contains aluminum, it is preferable to select aluminum as an arbitrary element existing only in the base material.
<Device>
X-ray photoelectron spectroscopy analyzer: ESCA-5500 manufactured by ULVAC-PHI
<Measurement conditions>
X-ray source; monochromatic AlKα ray photoelectron detection angle; 75 degree pass energy with respect to sample surface; 117.4 eV
Step energy; 0.5 eV / step
_{Sputter ion; C 60} ion spatter gun raster size with acceleration voltage of 10 kV ^{; 3 x 3 mm 2}
_{Spatter interval; 0.4 minutes Sputter rate of thermal oxide film (SiO 2} film) on silicon wafer of sputter gun; 2.20 nm / min Measurement pitch: 0.88 nm (converted to thermal oxide film on silicon wafer)

(Content of each element in the vapor deposition material)
3 to 10 g of the vapor-deposited material was sufficiently pulverized in advance, and the sample was made into a fine powder state and subjected to analysis of silicon, Group 5 element and alkali metal element.
<Silicon>
0.5 to 1.0 g of sodium hydroxide was taken in a zirconia crucible, melted with a burner, and allowed to cool. 100 mg of the finely pulverized sample was added onto this sodium hydroxide, and the sample was melted for 1 minute with a burner having a combustion temperature of about 600 ° C. After allowing to cool, the crucible was placed in a beaker or a plastic container. Pure water was added to the crucible and dissolved by heating. The dissolved solution was transferred to a beaker or a plastic container, and 20 mL of 6M hydrochloric acid was added at once. The volume was adjusted to 100 mL, and after dilution, the silicon content (mass%) was quantified by ICP emission spectroscopic analysis (measuring device PS3520U VDDII: product name, manufactured by Hitachi High-Tech Science Co., Ltd.). A calibration curve (matrix matching) method was used for quantification.
<Group 5 elements / alkali metal elements>
100 mg of the finely pulverized sample was decomposed with hydrofluoric acid-perchloric acid to remove silicon, and then solubilized with nitric acid or hydrochloric acid. The volume was adjusted to 100 mL, and after dilution, the content (% by mass) of the Group 5 element was quantified by ICP emission spectroscopic analysis (measuring device PS3520U VDDII: product name, manufactured by Hitachi High-Tech Science Co., Ltd.). The content (mass%) of the alkali metal element was quantified by the atomic absorption method (measuring device ZA3300: product name, manufactured by Hitachi High-Tech Science Co., Ltd.). A calibration curve (matrix matching) method was used for quantification.
Then, the ratio (mass ratio) of the content (mass%) of the target element to the silicon content (mass%) was calculated, and the molar ratio was obtained from the mass ratio using the atomic weight of each element.

(Abrasion resistance 1)
For the water- and oil-repellent layer, a steel wool bonster (count: # 0000, dimensions: 5 mm x 10 mm x) was used using a reciprocating traverse tester (manufactured by KNT) in accordance with JIS L0849: 2013 (ISO 105-X12: 2001). 10 mm) was reciprocated at a load of 9.8 N and a speed of 80 rpm. After the steel wool was worn 4,000 times, 6,000 times, and 10,000 times in a reciprocating manner, the contact angle of water in the water- and oil-repellent layer was measured, and the wear resistance was evaluated according to the following evaluation criteria.
A: Water contact angle is 100 degrees or more after 10,000 round trips B: Water contact angle is 100 degrees or more after 6,000 round trips or less than 10,000 times C: Round trip 4 Water contact angle is 100 degrees or more after 000 or more and less than 6,000 wear D: Water contact angle is less than 100 degrees after 4,000 reciprocating wear

(Abrasion resistance 2)
For the water- and oil-repellent layer, a steel wool bonster (count: # 0000, dimensions: 5 mm x 10 mm x) was used using a reciprocating traverse tester (manufactured by KNT) in accordance with JIS L0849: 2013 (ISO 105-X12: 2001). 10 mm) was reciprocated at a load of 9.8 N and a speed of 80 rpm. After the steel wool was worn 12,000 times in a reciprocating manner, the contact angle of water in the water-repellent and oil-repellent layer was measured, and the wear resistance was evaluated according to the following evaluation criteria. The smaller the decrease in the contact angle of water after wear, the smaller the decrease in performance due to wear, and the better the wear resistance.
A: Water contact angle is 105 degrees or more B: Water contact angle is 100 degrees or more and less than 105 degrees C: Water contact angle is less than 100 degrees

(Abrasion resistance 3)
The same procedure as for wear resistance 3 was performed except that the number of round trips was changed to 16,000.
A: Water contact angle is 100 degrees or more B: Water contact angle is 90 degrees or more and less than 100 degrees C: Water contact angle is 80 degrees or more and less than 90 degrees D: Water contact angle is less than 80 degrees

[Synthesis of fluorine-containing compounds]
[Synthesis Example 1]
Compound 3-11A was obtained with reference to the method for producing compound (ii-2) described in International Publication No. 2014/126064.
_{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 formula 3-11A
The average value of the number of units n: 13, the number average molecular weight of compound 3-11A: 4,920.

[Synthesis Example 2]
Compound 3-11B was obtained according to the method described in Example 3 of WO 2017/038832.
_{CF 3 - (OCF 2 CF 2} -OCF 2 CF 2 CF 2 CF 2) x3 (OCF 2 CF 2) -OCF 2 CF 2 CF 2 -CH 2 -N [CH 2 CH 2 CH 2 -Si (OCH 3) ₃ ] Type _{2 3-11B}
Average value of the number of units x3: 13, Mn of compound 3-11B: 5,020

[Synthesis Example 3]
Compound 3-11C was obtained according to the method described in Example 11-3 of WO 2017/038830.
CF _3- (OCF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ ) _n (OCF ₂ CF ₂ ) -OCF ₂ CF ₂ CF _2- C (O) NH-CH _2- C [CH ₂ CH ₂ CH _2- Si (OCH ₃ ) ₃ ] ₃ formula 3-11C
Average value of the number of units n: 13, Mn of compound 3-11C: 5,400

[Synthesis Example 4]
(Synthesis Example 4-1)
Compound X4-1 was obtained according to the method described in Example 2 of Example 2 of WO 2013/121984 (specifically, Example 2-3).
CF ₃ (OCF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ ) _m OCF ₂ CF ₂ OCF ₂ CF ₂ CF _2- C (O) OCH ₃ formula X4-1
Average value of the number of units m: 13

(Synthesis Example 4-2)
15 g of compound X4-1, 50 g of Asahiclean AK-225 (product name, manufactured by AGC), and 7.5 g of 2.0 M ammonia-methanol solution were placed in a 100 mL pressure resistant reactor, and the mixture was stirred at room temperature for 6 hours. Then, the solvent was distilled off to obtain 14.8 g (yield 99%) of the target compound X4-2.
_{CF 3 - (OCF 2 CF 2} OCF 2 CF 2 CF 2 CF 2) m -OCF 2 CF 2 -OCF 2 CF 2 CF 2 -C (O) -NH 2 Formula X4-2

NMR spectrum of compound X4-2:
¹⁹ F-NMR: -55 (3F), -82 (53F), -87 (53F), -90 (2F), -119 (2F), -123 to -128 (55F)

(Synthesis Example 4-3)
To a 300 mL eggplant flask, 15 g of compound X4-2, 75 g of AK-225, and 30 g of diethyl ether were added, and the mixture was stirred under an ice bath. Then, 0.31 g of lithium aluminum hydride was slowly added, and the mixture was stirred at room temperature for 20 hours. Then, 0.3 mL of a saturated aqueous solution of sodium sulfate was added, and the precipitated solid was removed by filtration through Celite. The obtained filtrate was concentrated and then purified by silica gel column chromatography to obtain 6.8 g (yield 45%) of the target compound X4-3.
_{CF 3 - (OCF 2 CF 2} OCF 2 CF 2 CF 2 CF 2) m -OCF 2 CF 2 -OCF 2 CF 2 CF 2 -CH 2 -NH 2 formula X4-3

NMR spectrum of compound X4-3:
^{1 1} H-NMR: 3.2 (2H)
¹⁹ F-NMR: -55 (3F), -82 (59F), -87 (59F), -90 (2F), -122 (2F), -123 to -128 (61F)

(Synthesis Example 4-4)
To a 50 mL eggplant flask, 0.2 g of HO (C = O) C (CH ₂ CH = CH ₂ ) ₃ , 10 mL of dichloromethane, and 0.2 mL of oxalyl chloride were added and stirred under ice-cooling, and then DMF (N, 0.0118 g of N-dimethylformamide) was added. Then, the mixture was stirred at room temperature for 3 hours and then concentrated to obtain 0.18 g of _{Cl (C = O) C (CH 2} CH = CH ₂ ) _3.
Separately, add 3.0 g of compound X4-3 and 0.35 mL of triethylamine to a 50 mL eggplant flask, and add Cl (C = O) C (CH ₂ CH = CH ₂ ) ₃ and 1,3-bistrifluoromethylbenzene 2 mL. Was added. The mixture was stirred for 1 hour and the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography to obtain 1.7 g (yield 54%) of compound X4-4.
_{CF 3 - (OCF 2 CF 2} OCF 2 CF 2 CF 2 CF 2) m -OCF 2 CF 2 -OCF 2 CF 2 CF 2 -CH 2 -NH-C (O) -C (CH 2 CH = CH 2) Type _{3 X4-4}

NMR spectrum of compound X4-4:
^{1 1} H-NMR: 6.1 (1H), 5.8 (3H), 5.2 (6H), 4.1 (2H), 2.4 (6H)
¹⁹ F-NMR: -55 (3F), -82 (49F), -87 (51F), -120 (2F), -126 (49F)

(Synthesis Example 4-5)
1.0 g of compound X4-4, xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in a nitrogen-substituted 50 mL eggplant flask (platinum content: 3% by mass) 0.003 g of aniline, 0.0009 g of aniline, and 1.0 g of AC-6000 (product name, manufactured by AGC) were added, 0.11 g of trimethoxysilane was added, and the mixture was stirred at 40 ° C. for 4 hours. After that, the same amount of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content: 3% by mass), aniline, and AC-6000 were further added, and the mixture was stirred for 7 hours. Then, the solvent was distilled off to obtain 1.1 g (yield 95%) of compound 3-11D.
_{CF 3 - (OCF 2 CF 2} OCF 2 CF 2 CF 2 CF 2) m -OCF 2 CF 2 -OCF 2 CF 2 CF 2 -CH 2 -NH-C (O) -C [CH 2 CH 2 CH 2 - Si (OCH ₃ ) ₃ ] ₃ formula 3-11D

NMR spectrum of compound 3-11D:
^{1 1} H-NMR: 6.0 (1H), 4.1 (2H), 3.6 (27H), 1.7 (6H), 1.4 (6H), 0.7 (6H)
¹⁹ F-NMR: -55 (3F), -82 (49F), -87 (51F), -120 (2F), -126 (49F)
Average value of the number of units m: 13

[Synthesis Example 5]
Compound 3-11E was obtained according to the method described in Synthesis Example 15 of Japanese Patent No. 5761305.
_{CF 3 - (OCF 2 CF 2} ) 15 (OCF 2) 16 -OCF 2 CH 2 -OCH 2 CH 2 CH 2 -Si [CH 2 CH 2 CH 2 Si (OCH 3) 3] 3 expression 3-11E
Compound 3-11E Mn: 3,600

[Synthesis Example 6]
Compound 3-21A was synthesized by the following procedure.

In a nitrogen-substituted reactor, 21.8 g of NaH weighed in a nitrogen-substituted box was put into 100 g of dehydrated THF (tetrahydrofuran), stirred in an ice bath, and 50 mass in which malononitrile of dehydrated THF was dissolved. After adding 40 g of the tetrahydrofuran nitrile solution, 80.6 g of allyl bromide was added and stirred in an ice bath for 4 hours. A dilute aqueous hydrochloric acid solution was added to stop the reaction, and the mixture was washed with water and saturated brine, and the organic phase was recovered. The recovered solution was concentrated on an evaporator to obtain a crude product. The crude product was developed by silica gel column chromatography to separate 42 g of compound X6-1.

式Ｘ６−１

Equation X6-1

_{31.1 g of LiAlH 4} and 100 g of dehydrated THF were added to a nitrogen-substituted eggplant flask having a capacity of 300 mL, and the mixture was stirred in an ice bath until the temperature reached 0 ° C. 40 g of compound X6-1 was slowly added dropwise. After confirming the disappearance of compound X6-1 by thin layer chromatography, Na ₂ SO ₄・ 10H ₂ O was slowly added to the reaction crude solution for quenching, filtered through Celite, and washed with water and saturated brine. .. The recovered organic layer was distilled off under reduced pressure and purified by column chromatography to obtain 32.5 g of compound X6-2.

式Ｘ６−２

Equation X6-2

In a 50 mL eggplant flask, 0.4 g of compound X6-2 and CF ₃ (OCF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ ) ₁₃ OCF ₂ CF ₂ OCF ₂ CF ₂ CF _2- C (O) -CH ₃ 27 g of the above was added, and the mixture was stirred for 12 hours. From NMR, it was confirmed that all of compound X6-2 was converted to compound X6-3. In addition, methanol, which is a by-product, was produced. The obtained solution was diluted with 9.0 g of AE-3000 and purified by silica gel column chromatography (developing solvent: AE-3000) to obtain 16.3 g (yield 66%) of compound X6-3.
In the following formula, the PFPE is CF ₃ (OCF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ ) ₁₃ OCF ₂ CF ₂ OCF ₂ CF ₂ CF _2- .

式Ｘ６−３

Equation X6-3

In a 100 mL PFA eggplant flask, 5.0 g of compound X6-3 and a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%). Add 0.5 g, 0.3 g of HSi (OCH ₃ ) ₃ , 0.02 g of dimethyl sulfoxide and 5.0 g of 1,3-bis (trifluoromethyl) benzene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) at 40 ° C. The mixture was stirred for 10 hours. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter having a pore size of 0.2 μm to obtain compound 3-21A in which the two allyl groups of compound X6-3 were hydrosilylated. The conversion rate of hydrosilylation was 100%, and compound X6-3 did not remain.
In the following formula, PFPE is CF ₃ (OCF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ ) ₁₃ OCF ₂ CF ₂ OCF ₂ CF ₂ CF _2- , and Me is a methyl group.

式３−２１Ａ

Equation 3-21A

Mn: 9,800 of Compound 3-21A

[Synthesis Example 7]
Compound 3-31A was obtained according to Example 4 of JP-A-2015-199906.

式３−３１Ａ

Equation 3-31A

In the above formula 3-31A, p1: q1≈47: 53 and p1 + q1≈43.
Mn of Compound 3-31A: 4,800

[Synthesis Example 8]
Compound 3-31B was synthesized by the following procedure.
(Synthesis Example 8-1)
Compound X8-1 was obtained according to the method described in Example 1-1 of Examples of WO 2013-121984.
CF ₂ = CFO-CF ₂ CF ₂ CF ₂ CH ₂ OH formula X8-1

(Synthesis Example 8-2)
In a 200 mL eggplant flask, _{16.2 g of HO-CH 2} CF ₂ CF ₂ CH _2- OH and 13.8 g of potassium carbonate were placed, stirred at 120 ° C., 278 g of compound X8-1 was added, and the temperature was 120 ° C. The mixture was stirred for 2 hours. Back to 25 ℃, AC-2000 (product name, AGC _Corp., C _{6 F 13} H) and hydrochloric acid were placed 50g each, were separated, the organic phase was concentrated. The obtained crude reaction solution was purified by column chromatography to obtain 117.7 g (yield 40%) of compound X8-2.

式Ｘ８−２

Equation X8-2

NMR spectrum of compound X8-2;
^{1 1} H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: tetramethylsilane (TMS)) δ (ppm): 6.0 (12H), 4.6 (20H), 4.2 (4H), 4 .1 (4H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -85 (24F), -90 (24F), -120 (20F), -122 (4F), -123 (4F), -126 (24F), -144 (12F)
Average value of the number of units m + n: 10.

(Synthesis Example 8-3)
In a 50 mL eggplant flask connected to a reflux condenser, 20 g of compound X8-2 obtained in Synthesis Example 8-2, 2.4 g of sodium fluoride powder, 20 g of AC-2000, CF ₃ CF ₂ CF ₂ OCF ( CF ₃ ) 18.8 g of COF was added. The mixture was stirred at 50 ° C. for 24 hours under a nitrogen atmosphere. After cooling to room temperature, sodium fluoride powder was removed with a pressure filter, and excess CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF and AC-2000 were distilled off under reduced pressure to obtain 24 g of compound X8-3. (Yield 100%) was obtained.

式Ｘ８−３

Equation X8-3

NMR spectrum of compound X8-3;
^{1 1} H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: tetramethylsilane (TMS)) δ (ppm): 6.0 (12H), 5.0 (4H), 4.6 (20H), 4 .2 (4H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -79 (4F), -81 (6F), -82 (6F), -85 (24F), -90 (24F), 119 (4F), -120 (20F), -122 (4F), -126 (24F), -129 (4F), -131 (2F), -144 (12F).
Average value of the number of units m + n: 10.

(Synthesis Example 8-4)
_{250 mL of ClCF 2} CFClCF ₂ OCF ₂ CF ₂ Cl (hereinafter referred to as "CFE-419") was placed in a 500 mL nickel reactor, and nitrogen gas was bubbled. After the oxygen gas concentration was sufficiently lowered, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled for 1 hour. A CFE-419 solution of compound X8-3 obtained in Synthesis Example 8-3 (concentration: 10% by mass, compound X8-3: 24 g) was added over 6 hours. The ratio of the introduction rate of fluorine gas (mol / hour) to the introduction rate of hydrogen atoms in compound X8-3 (mol / hour) was controlled to be 2: 1. After the addition of compound X8-3 was completed, a CFE-419 solution of benzene (concentration: 0.1% by mass, benzene: 0.1 g) was added intermittently. After the addition of benzene was completed, the fluorine gas was bubbled for 1 hour, and finally the inside of the reactor was sufficiently replaced with nitrogen gas. The solvent was distilled off to obtain 25.3 g (yield 90%) of compound X8-4.

式Ｘ８−４

Equation X8-4

NMR spectrum of compound X8-4;
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -79 (4F), -81 (6F), -82 (6F), -83 (48F), -87 (44F), -124 (48F), -129 (4F), -131 (2F).
Average value of the number of units m + n: 10.

(Synthesis Example 8-5)
In a 50 mL eggplant flask, 25.3 g of compound X8-4 obtained in Synthesis Example 8-4, 2.2 g of sodium fluoride, and 25 mL of AC-2000 were placed and stirred in an ice bath. 1.7 g of methanol was added and stirred at 25 ° C. for 1 hour. After filtration, the filtrate was purified by column chromatography. 15 g (yield 80%) of compound X8-5 was obtained.

式Ｘ８−５

Formula X8-5

NMR spectrum of compound X8-5;
^{1 1} H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: tetramethylsilane (TMS)) δ (ppm): 4.2 (6H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -83 (44F), -87 (44F), 119 (4F), -124 (44F).
Average value of the number of units m + n: 10.

(Synthesis Example 8-6)
In a 50 mL eggplant flask, 15 g of compound X8-5 obtained in Synthesis Example 8-5, 3.2 g of H ₂ NCH ₂ C (CH ₂ CH = CH ₂ ) ₃ , and 15 mL of AC-2000 were placed at 0 ° C. Was stirred for 24 hours. The crude reaction solution was purified by column chromatography and separated into three fractions containing the desired product. A total of 11.2 g (yield 70%) of compound X8-6 was obtained. The fractions of each of the three types were C4-6a, C4-6b, and C4-6c. Further, the fraction C4-6c was purified again by column chromatography to obtain a fraction C4-6d.
The fractions C4-6a to C4-6c contained compound X8-6 and compound X8-7. Then, the ratio (CF ₃ / CF ₂ ) was determined ^{by 19} F-NMR using each fraction. Incidentally, CF ₃ in a ratio means the number of moles of -CF ₃ group at one end of the compound X8-7 (-CF ₃ group within the dotted line frame in the ^formula), the 19 F-NMR -85 Observed at -87 ppm. Further, CF ₂ in the ratio is at one end near the compound X8-7 -CF ₂ - group (-CF ₂ within the dotted line frame in the formula - group) and, in the vicinity of both ends of the compound X8-6 there -CF ₂ - group (-CF ₂ within the dotted line frame in the formula - group) and means the total number of moles ^of, is observed -120ppm in 19 F-NMR. It was confirmed that compound X8-7 was not detected in the fraction C4-6d.
_{CF 3} / CF ₂ = 0.11 in fraction C4-6a
_{CF 3} / CF ₂ = 0.06 in fraction C4-6b
_{CF 3} / CF ₂ = 0.05 in fraction C4-6c

式Ｘ８−６

Formula X8-6

NMR spectrum of compound X8-6;
^{1 1} H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: tetramethylsilane (TMS)) δ (ppm): 6.1 (6H), 5.2 (12H), 3.4 (4H), 2 .1 (12H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -83 (44F), -87 (44F), -120 (4F), -124 (44F).
Average value of the number of units m + n: 10.

式Ｘ８−７

Formula X8-7

(Synthesis Example 8-7)
In a 50 mL eggplant flask, 1 g of the distillate C4-6a obtained in Synthesis Example 8-6, 0.21 g of trimethoxysilane, 0.001 g of aniline, 1.0 g of AC-6000, platinum / 1,3- 0.0033 g of divinyl-1,1,3,3-tetramethyldisiloxane complex was added, and the mixture was stirred at 25 ° C. overnight. The solvent and the like were distilled off under reduced pressure to obtain 1.2 g (yield 100%) of the mixture M1.
The mixture M1 contained compound 3-11E and compound 3-31B.
Using the mixture M1 _{, the ratio (CF 3} / CF ₂ ) was determined ^{by 19} F-NMR in the same manner as in Synthesis Example 8-6. The groups in the dotted frame in the formula are the groups to be measured by ^{19 F-NMR.}
_{CF 3} / CF ₂ = 0.11 in mixture M1

式３−１１Ｅ

Equation 3-11E

式３−３１Ｂ

Equation 3-31B

NMR spectrum of compound 3-31B;
^{1 1} H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: tetramethylsilane (TMS)) δ (ppm): 3.6 (54H), 3.4 (4H), 1.3 (24H), 0 .9 (12H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -83 (44F), -87 (44F), -120 (4F), -124 (44F).
Average value of the number of units m + n: 10, Mn of compound 3-31B: 4,950

In the mixture M1 obtained as described above, compound 1-1D and compound 3-31B were separated by molecular distillation to obtain compound 3-31B.

[Synthesis Example 9]
Compound 3-11B and compound 3-21A were mixed at a mass ratio of 1: 1 to obtain a mixture M2.

[Synthesis Example 10]
Compound 3-11B and compound 3-31A were mixed at a mass ratio of 1: 1 to obtain a mixture 3.

[Synthesis Example 11]
Compound 3-11C and compound 3-31B were mixed at a mass ratio of 1: 1 to obtain a mixture 4.

[Example 1]
Eirich Intensive Mixer EL-1 (manufactured by Japan Eirich, hereinafter referred to as "EL-1" _{), 27 g of niobium oxide (manufactured by Sigma-Aldrich, Nb 2} O ₅ ), and amorphous silica SC5500-SQ (commodity). 242 g of (name, manufactured by Admatex) was added, and the mixture was stirred and mixed at 2400 rpm for 30 seconds. The stirring speed was changed to 4800 rpm, 40 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 600 rpm for 5 minutes. The obtained particles were taken out from EL-1 and vacuum dried at 150 ° C. for 30 minutes to obtain a granulated material, and then the granulated material was baked at 1,000 ° C. for 1 hour to obtain a sintered body 1. ..
10 g of sintered body 1 and 0.5 g of compound 3-11A were placed as a vapor deposition material (vapor deposition source) on a molybdenum boat in a vacuum vapor deposition apparatus (VTR-350M manufactured by ULVAC Kiko Co., Ltd.). A glass substrate (Dragonrail (registered trademark) manufactured by AGC Inc.) was placed in the vacuum vapor deposition apparatus, and the inside of the vacuum vapor deposition apparatus was exhausted until the pressure became ^{5 × 10 -3 Pa or less.}
The boat on which the sintered body 1 was placed was heated to 2,000 ° C. and vacuum-deposited on a glass substrate to form a base layer having a thickness of 10 nm.
Further, the boat on which the compound 3-11A was placed was heated to 700 ° C., and the compound 3-11A was vacuum-deposited on the surface of the base layer to form a water-repellent and oil-repellent layer having a thickness of 10 nm. In this way, the base material with the water-repellent and oil-repellent layer of Example 1 was obtained.

[Example 2]
_{Tantalum pentoxide (Ta 2} O ₅ manufactured by Sigma-Aldrich) was used instead of niobide oxide, and the ratio of the total molar concentration of Group 5 elements to the molar concentration of silicon in the sintered body is the value shown in Table 1. The base material with the water-repellent and oil-repellent layer of Example 2 was formed in the same manner as in Example 1 except that the sintered body obtained by adjusting the amounts of tantalum oxide and amorphous silica used was used.

[Example 3]
Vanadium oxide in place of niobium oxide (Sigma-Aldrich Corp., V 2 _{O 5)} with, to the molar concentration of silicon in the sintered body, the ratio of the total molar concentration of the Group 5 element values shown in Table 1 The base material with the water-repellent and oil-repellent layer of Example 3 was formed in the same manner as in Example 1 except that the sintered body obtained by adjusting the amounts of vanadium oxide and amorphous silica used was used.

[Examples 4 to 7]
Sintering obtained by adjusting the amounts of niobium oxide and amorphous silica used so that the ratio of the total molar concentration of Group 5 elements to the molar concentration of silicon in the sintered body becomes the value shown in Table 1. The base material with the water- and oil-repellent layer of Examples 4 to 7 was formed in the same manner as in Example 1 except that the body was used.

[Examples 8 to 17]
Substrate with water-repellent and oil-repellent layer of Examples 8 to 17 was obtained in the same manner as in Example 1 except that the compounds or mixtures shown in Table 1 were used instead of Compound 3-11A as the fluorine-containing compound.

[Example 18]
To EL-1, 27 g of niobium oxide (manufactured by Sigma-Aldrich, Nb ₂ O ₅ ), 19 g of soda ash (manufactured by Soda Ash Japan), and 242 g of amorphous silica are added and stirred at 2400 rpm for 30 seconds. Mixed. The stirring speed was changed to 4800 rpm, 45 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 600 rpm for 5 minutes. The obtained particles were taken out from EL-1, dried at 150 ° C. for 30 minutes, and further fired at 1,000 ° C. for 1 hour to obtain a sintered body.
The base material with the water-repellent and oil-repellent layer of Example 18 was formed in the same manner as in Example 8 except that the obtained sintered body was used instead of the sintered body 1.

[Example 19]
The base material with the water-repellent and oil-repellent layer of Example 19 was formed in the same manner as in Example 9 except that the sintered body obtained in Example 18 was used instead of the sintered body 1.

[Example 20]
To 20 g of an isopropyl alcohol solution of 0.347 mass% tetraethyl orthosilicate (manufactured by Wako Pure Chemical Industries, Ltd.) and a methanol solution (high purity) of _{0.03 mass% pentaethyl niobate (Nb (OC 2} H ₅ ) _5). 20 g of (manufactured by Chemical Industries, Ltd.) was added and stirred for 10 minutes to obtain a coating solution for forming an underlayer.
One surface of a glass substrate (Dragonrail (registered trademark), manufactured by AGC) was subjected to corona discharge treatment under the conditions of 80 V and 3.5 A using a high frequency power supply (CG102A: product name, manufactured by Kasuga Electric Co., Ltd.).
A coating liquid for forming a base layer is applied to the corona discharge-treated surface of a glass substrate by a spin coating method under the conditions of a rotation speed of 3,000 rpm and a rotation time of 20 seconds to form a wet film, and then wet. The film was baked at 300 ° C. for 30 minutes to form a base material with a base layer (thickness of the base layer was 10 nm).
0.5 g of compound 3-11A was placed as a vapor deposition material (deposited source) on a molybdenum boat in a vacuum vapor deposition apparatus (VTR-350M: product name, manufactured by ULVAC Kiko Co., Ltd.). A base material with a base layer was placed in the vacuum vapor deposition apparatus, and the inside of the vacuum vapor deposition apparatus was exhausted until the pressure became ^{5 × 10 -3 Pa or less.} The boat was heated to 700 ° C., and compound 3-11A was vacuum-deposited on the surface of the base layer to form a water- and oil-repellent layer having a thickness of 10 nm. In this way, the base material with the water-repellent and oil-repellent layer of Example 20 was obtained.

[Example 21]
30 g of silicon oxide (manufactured by Canon Optron) and 5 g of compound 3-11A were placed as a vapor deposition material (vapor deposition source) on a molybdenum boat in a vacuum vapor deposition apparatus (VTR-350M manufactured by ULVAC Kiko Co., Ltd.). A glass substrate was placed in the vacuum vapor deposition apparatus, and the inside of the vacuum vapor deposition apparatus was exhausted until the pressure became ^{5 × 10 -3 Pa or less.}
The boat on which silicon oxide was placed was heated to 2,000 ° C. and vacuum-deposited on a glass substrate to form a base layer having a thickness of 10 nm.
Further, the boat on which the compound 3-11A was placed was heated to 700 ° C., and the compound 3-11A was vacuum-deposited on the surface of the base layer to form a water-repellent and oil-repellent layer having a thickness of 10 nm. In this way, the base material with the water-repellent and oil-repellent layer of Example 21 was obtained.

[Examples 22 to 23]
Sintering obtained by adjusting the amounts of niobium oxide and amorphous silica used so that the ratio of the total molar concentration of Group 5 elements to the molar concentration of silicon in the sintered body becomes the value shown in Table 1. The base material with the water- and oil-repellent layer of Examples 22 to 23 was formed in the same manner as in Example 1 except that the body was used.

For each of the above examples, the above-mentioned physical property measurement and evaluation test were performed. The evaluation results are shown in Table 1.
In the table, "Group 5 element / silicon (molar ratio)" refers to the Group 5 element in the vapor deposition material, coating liquid or base layer with respect to the molar concentration of silicon in the vapor deposition material, coating liquid or base layer. Means the ratio of total molarities.

As shown in Table 1, the ratio of the molar concentration of the Group 5 element in the underlying layer to the molar concentration of silicon in the underlying layer, which contains silicon and oxides containing Group 5 elements in the periodic table, is 0.005. It was confirmed that a base material with a water-repellent oil-repellent layer having excellent wear resistance of the water-repellent oil-repellent layer could be obtained by using a base layer of about 2.00.

The base material with a water-repellent oil-repellent layer of the present invention can be used for various applications in which water-repellent and oil-repellent properties are required. For example, display input devices such as touch panels; transparent glass or transparent plastic members, lenses for glasses, antifouling members for kitchens; water- and moisture-repellent members such as electronic devices, heat exchangers, and batteries, and antifouling members. Antifouling member for toiletry; Member that requires liquid repellency while conducting; Water-repellent / waterproof / water-sliding member of heat exchanger; Can be used for vibration sieve, surface low friction member such as inside cylinder. More specific examples of use include a display front protective plate, an antireflection plate, a polarizing plate, an antiglare plate, or an antiglare coating on the surface thereof, a mobile phone (for example, a smartphone), or a mobile information terminal. , Game machines, devices such as remote controls, touch panel sheets, touch panel displays, and other devices that have display input devices that operate on the screen with human fingers or palms (for example, glass or film used for display units, etc., and Glass or film used for exterior parts other than the display part). In addition to the above, decorative building materials around water such as toilets, baths, washrooms, kitchens; waterproof members for wiring boards; water-repellent / waterproof / sliding members for heat exchangers; water-repellent members for solar cells; printed wiring boards Waterproof / water-repellent material; Waterproof / water-repellent material for electronic device housings and electronic parts; Material for improving the insulation of transmission lines; Waterproof / water-repellent material for various filters; Waterproofing members; Antifouling members for baths, kitchen equipment, toiletries; Surface low friction members such as vibrating sieves and cylinders; Mechanical parts, vacuum equipment parts, bearing parts, parts for transportation equipment such as automobiles; Tools, etc. Examples include surface protection members.

10 Base material with water-repellent and oil-repellent layer 12 Base material 14 Base layer 16 Water- and oil-repellent layer

Claims (10)

A base material with a water-repellent oil-repellent layer having a base material, a base layer, and a water-repellent oil-repellent layer in this order.
The water- and oil-repellent layer is composed of a condensate of a fluorine-containing compound having a reactive silyl group.
The underlayer contains an oxide containing silicon and Group 5 elements of the Periodic Table.
A base material with a water- and oil-repellent layer, wherein the ratio of the total molar concentration of Group 5 elements in the base layer to the molar concentration of silicon in the base layer is 0.005 to 2.00. The base material with a water-repellent and oil-repellent layer according to claim 1, wherein the Group 5 element is at least one element selected from the group consisting of vanadium, niobium and tantalum. The base material with a water-repellent oil-repellent layer according to claim 1 or 2, wherein the oxide further contains an alkali metal element. Contains oxides containing silicon and Group 5 elements of the Periodic Table
A vapor deposition material in which the ratio of the total molar concentration of Group 5 elements in the periodic table to the molar concentration of silicon is 0.005-2.00. The vapor-deposited material according to claim 4, wherein the Group 5 element is at least one element selected from the group consisting of vanadium, niobium and tantalum. The vapor-deposited material according to claim 4 or 5, wherein the oxide further contains an alkali metal element. The oxide further comprises at least one element I selected from the group consisting of nickel, iron, titanium, zirconium, molybdenum, and tungsten.
The vapor-deposited material according to any one of claims 4 to 6, wherein the ratio of the total molar concentration of the element I to the molar concentration of silicon is 0.01 or less. The vapor-deposited material according to any one of claims 4 to 7, which is a molten material, a sintered body, or a granulated material. A method for producing a base material with a water-repellent oil-repellent layer having a base material, a base layer, and a water-repellent oil-repellent layer in this order.
By the vapor deposition method using the vapor deposition material according to any one of claims 4 to 8, the base material contains silicon and an oxide containing a Group 5 element of the periodic table, and silicon in the base layer. The base layer is formed in which the ratio of the total molar concentration of the Group 5 elements in the base layer to the molar concentration of is 0.005 to 2.00.
Next, a method for producing a base material with a water-repellent oil-repellent layer, which forms the water-repellent oil-repellent layer made of a condensate of a fluorine-containing compound having a reactive silyl group on the base layer. A method for producing a base material with a water-repellent oil-repellent layer having a base material, a base layer, and a water-repellent oil-repellent layer in this order.
By a wet coating method using a coating liquid containing a compound containing silicon, a compound containing a Group 5 element of the periodic table, and a liquid medium, silicon and a Group 5 element of the periodic table are placed on the substrate. The underlayer is formed by containing an oxide and having a ratio of the total molar concentration of Group 5 elements in the underlayer to the molar concentration of silicon in the underlayer of 0.005 to 2.00.
Next, a method for producing a base material with a water-repellent oil-repellent layer, which forms the water-repellent oil-repellent layer made of a condensate of a fluorine-containing compound having a reactive silyl group on the base layer.

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