JP2021035725A - Article with functional layer and method for manufacturing article with functional layer - Google Patents

Abstract

To provide an article with a functional layer having excellent durability by suppressing reduction in the performance of the functional layer with time.SOLUTION: The article with a functional layer includes a substrate and a functional layer laminated on the substrate, in which the functional layer comprises an intermediate layer containing silicon oxide and aluminum oxide and a surface layer directly laminated on the intermediate layer and formed by using an organic compound having a group that can react with silicon oxide and aluminum oxide. In depth points of a profile in a depth direction of the functional layer obtained by X-ray photoelectron spectroscopy, when a depth point where the proportion of C atoms to the total number of C atoms, O atoms, Al atoms and Si atoms first reaches 5 atom% or less is defined as a start point, an average of the proportion of Al atoms in the depth direction with respect to the total number of Si atoms and Al atoms in the region at 1.0 nm or more and 3.0 nm or less distance from the start point in the depth direction is 55 atom% or more and 98 atom% or less.SELECTED DRAWING: Figure 1

Description

The present invention relates to an article with a functional layer and a method for producing an article with a functional layer.

Conventionally, in order to modify the surface of various base materials, a technique of providing a layer having a desired performance on the base material has been known. As a method for forming the above layer, a method is known in which a compound having a desired performance and having a group capable of reacting with a base material is reacted with the base material.

In Patent Document 1, in a technique for providing a surface coating on a single crystal sapphire base layer, a transition layer containing alumina and silica and having a silica content of 50% or more on the surface layer is provided on the base layer. The technology is described.

Special Table 2016-500030 Gazette

However, the present inventors have good film forming property of the layer and sufficient performance can be obtained in the initial state in the article obtained by using the known technique, but it is caused by the durability of the layer during use. It was found that the performance disappeared.

The present invention has been made from the above viewpoint, and an object of the present invention is to provide an article with a functional layer having excellent durability by suppressing deterioration of the performance of the functional layer over time.

The present invention provides an article with a functional layer and a method for producing an article with a functional layer having the following configurations.
[1] An article with a functional layer having a base material and a functional layer laminated on the base material, wherein the functional layer is directly on an intermediate layer containing silicon oxide and aluminum oxide and the intermediate layer. It is composed of a laminated surface layer formed by using an organic compound having a group capable of reacting with silicon oxide and aluminum oxide, and the depth direction of the functional layer obtained by X-ray photoelectron spectroscopy. At each depth point in the profile, the starting point is the depth point where the ratio of carbon atoms to the total number of carbon atoms, oxygen atoms, aluminum atoms, and silicon atoms is 5 atomic% or less for the first time, and the depth direction is from the starting point. The average value in the depth direction of the ratio of aluminum atoms to the total number of silicon atoms and aluminum atoms in the region of 1.0 nm or more and 3.0 nm or less is 55 atomic% or more and 98 atomic% or less. An article with a functional layer.
[2] The organic compound is an article with a functional layer according to [1], which contains a fluorine-containing compound.
[3] The fluorine-containing compound is the article with a functional layer according to [2], which has a poly (oxyperfluoroalkylene) chain.
[4] An article having a functional layer according to any one of [1] to [3], wherein the base material is sapphire.
[5] An intermediate layer containing silicon oxide and aluminum oxide is formed on the surface of the base material, and an organic compound having a group capable of reacting with silicon oxide and aluminum oxide is wet-coated or dry-coated on the intermediate layer. A method for obtaining an article with a functional layer having a functional layer including the intermediate layer and the surface layer directly laminated on the intermediate layer, wherein the surface layer is formed by the above method, and X-ray photoelectron spectroscopy in the functional layer. Starting from the depth point where the ratio of carbon atoms to the total number of carbon atoms, oxygen atoms, aluminum atoms, and silicon atoms became 5 atomic% or less for the first time at each depth point of the depth direction profile obtained by the method. The average value in the depth direction of the ratio of aluminum atoms to the total number of silicon atoms and aluminum atoms in the region of 1.0 nm or more and 3.0 nm or less in the depth direction from the starting point is 55 atom% or more and 98 atoms. % Or less, a method for producing an article with a functional layer.

According to the present invention, it is possible to provide an article with a functional layer having excellent durability by suppressing a decrease in the performance of the functional layer over time.

It is sectional drawing which shows typically the article with a functional layer.

In the present specification, the compound represented by the formula 1 is referred to as compound 1. Compounds represented by other formulas are also described in the same manner. The group represented by the formula 1 is referred to as the group 1. The groups 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 an alkylene group. It may have an A group at the end, such as −A group−.
In the present specification, "~" representing a numerical range includes upper and lower limits.

The meanings of the following terms in the present specification are as follows.
The "hydrolyzable silyl group" means a group capable of forming a silanol group (Si-OH) by a hydrolyzing reaction. For example, −SiR _n L _3-n in Equation 1.
The "ethery oxygen atom" means an oxygen atom that forms an ether bond (-O-) between carbon atoms. The chemical formula of the oxyperfluoroalkylene group shall be expressed by describing the oxygen atom on the right side of the perfluoroalkylene group.

The "divalent organopolysiloxane residue" is a group represented by the following formula. ^Ra 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 ^b ) ₂ PhSi (R ^b ) _2- (where Ph is a phenylene group and R ^b is a monovalent organic group). Is. As R ^b , an alkyl group (preferably 1 to 10 carbon atoms) is preferable.
A "dialkylsilylene group" is a group represented by −Si (R ^c ) _2- (where R ^c is an alkyl group (preferably having 1 to 10 carbon atoms)).
The "number average molecular weight" of the fluorine-containing ether compound is calculated by obtaining the number (average value) of oxyperfluoroalkylene groups based on the terminal groups by ¹ H-NMR and ^{19 F-NMR using NMR analysis method.} Will be done.

The "coating film" is a film before drying obtained by applying a composition containing a liquid medium, and is a film containing a liquid medium. That is, in the present specification, the coating film and the film (layer) obtained by removing the liquid medium by drying the coating film are distinguished.

[Article with functional layer]
The article with a functional layer of the present invention has a base material and a functional layer laminated on the base material.
The functional layer in the present invention comprises an intermediate layer laminated on the base material and a surface layer directly laminated on the intermediate layer. That is, of the two layers constituting the functional layer, the intermediate layer exists on the base material side and the surface layer exists on the air side. The intermediate layer contains silicon oxide and aluminum oxide, and the surface layer is formed using an organic compound having a group capable of reacting with silicon oxide and aluminum oxide.
The "layer laminated on the base material" is not limited to the case where the layer is directly laminated on the base material, but also includes the case where another layer is provided between the base material and the layer, and has the following configuration. Is the same.

In the functional layer of the present invention, the ratio of carbon atoms to the total number of carbon atoms, oxygen atoms, aluminum atoms, and silicon atoms is 5 atoms for the first time at each depth point of the depth direction profile obtained by X-ray photoelectron spectroscopy. A depth point of% or less is defined as a starting point (hereinafter, also referred to as “starting point S”), and a region of 1.0 nm or more and 3.0 nm or less in the depth direction from the starting point S (hereinafter, also referred to as “region Q”). ), The average value of the ratio of aluminum atoms to the total number of silicon atoms and aluminum atoms in the depth direction is 55 atomic% or more and 98 atomic% or less.

In the above, the ratio of carbon atoms to the total number of carbon atoms, oxygen atoms, aluminum atoms, and silicon atoms is also referred to as "C content", and the ratio of aluminum atoms to the total number of silicon atoms and aluminum atoms is also referred to as "Al content". Say.

In the functional layer, as described above, the surface layer is a layer mainly composed of organic substances, and the intermediate layer is a layer containing inorganic substances. Therefore, if the C content at each point set at a predetermined interval from the outermost surface on the surface layer side of the functional layer is measured, the C content that maintains a predetermined value in the surface layer region is greatly reduced. The point where the C content is 5 atomic% or less (starting point S) can be recognized as the boundary between the surface layer and the intermediate layer. Thereby, the surface parallel to the main surface of the base material including the starting point S can be defined as the interface between the surface layer and the intermediate layer.

That is, in the functional layer, the surface from the outermost surface of the functional layer on the air side to the starting point S can be regarded as the surface layer, and the area from the starting point S to the interface between the functional layer and the base material can be regarded as an intermediate layer. Therefore, the region Q can be rephrased as a region in the intermediate layer having a depth of 1.0 nm or more and 3.0 nm or less in the thickness direction from the interface with the surface layer (hereinafter, also referred to as “surface layer region of the intermediate layer”). In the following description, the average value of the Al content in the region Q in the depth direction is referred to as "Al content in the surface region of the intermediate layer".

By having the above-mentioned structure, the article with a functional layer of the present invention is excellent in durability because the deterioration of the performance of the functional layer with time is suppressed. The reason for this is not always clear, but it is presumed as follows.

It is considered that the surface layer is strongly held on the intermediate layer by laminating the intermediate layer containing silicon oxide and aluminum oxide on the base material. Further, when the Al content in the surface layer region of the intermediate layer is within a predetermined range, the hardness of the intermediate layer and the interaction between the intermediate layer and the surface layer are balanced, so that the durability of the functional layer is improved. , It is considered that the performance of the functional layer is maintained at a high level.

FIG. 1 is a cross-sectional view schematically showing an example of an article with a functional layer according to an embodiment of the present invention. The article 10 with a functional layer according to the embodiment of the present invention shown in FIG. 1 has a plate-shaped base material 1 and a functional layer 4 laminated on one main surface 1a of the base material 1. The functional layer 4 has an intermediate layer 2 on the base material 1 side, and has a surface layer 3 on a main surface 2a on the side opposite to the surface of the intermediate layer 2 in contact with the base material 1.

As shown in FIG. 1, the article 10 with a functional layer may have a functional layer 4 only on one main surface 1a of the base material 1, and further has a functional layer 4 on the other main surface 1b or a side surface. You may. Further, when the functional layer 4 is provided only on one main surface 1a of the base material 1, the functional layer 4 may be provided on the entire surface thereof, or the functional layer 4 may be partially provided on the entire surface thereof. Further, in the functional layer 4, the surface layer 3 does not have to completely cover the intermediate layer 2. The location where the functional layer 4 is provided is appropriately adjusted according to the use of the article with the functional layer.

In the configuration of the article 10 with the functional layer, if necessary, between the base material 1 and the functional layer 4, the main surface 1b on the side opposite to the functional layer 4 of the base material 1 does not impair the effect of the present invention. Additional layers may be provided.

(Base material)
The base material in the present invention is not particularly limited as long as it is a base material that requires surface modification (giving a specific performance). Examples of the material of the base material include metal, resin, glass (which may be chemically strengthened), sapphire, ceramic, stone, and a composite material thereof. Among these, sapphire is preferable from the viewpoint that the effect of the present invention is more prominently exhibited.

The base material may have a single-layer structure or a laminated structure. The base material preferably has at least a main surface on which an intermediate layer is formed made of sapphire. In general, sapphire means _{α-Al 2} O _3. In the present specification, α-Al ₂ O ₃ crystals containing trace components (for example, SiO _{2 ) other than α-Al 2} O ₃ and α-Al ₂ O ₃ are also included in the category of “sapphire”.

The shape, size, etc. of the base material are not particularly limited. It is appropriately selected according to the use of the article with a functional layer described later.

From the viewpoint of further improving the adhesion between the base material and the functional layer, the surface of the base material may be subjected to an activation treatment (for example, a dry activation treatment or a wet activation treatment). Specific examples of the dry activation treatment include a treatment of irradiating the surface of a base material with active energy rays (for example, ultraviolet rays, electron beams, X-rays), a corona discharge treatment, a vacuum plasma treatment, a normal pressure plasma treatment, and a flame treatment. , Itro processing can be mentioned. Specific examples of the wet activation treatment include a treatment in which the surface layer is brought into contact with an acid or alkaline solution. Among the above activation treatments, the corona discharge treatment is preferable from the viewpoint of further improving the adhesion between the base material and the intermediate layer.

Further, a material having a further layer on the surface of the base material main body made of the above-mentioned material may be used as the base material. The layer may be a layer other than the functional layer of the present invention and the layer (intermediate layer and surface layer) of the functional layer of the present invention, but from the viewpoint of excellent effect of the present invention, adhesion to the base material body. A layer having excellent properties is preferable, and specific examples thereof include a diamond-like carbon layer and a silicon oxide layer.

The diamond-like carbon layer means a film having an amorphous structure in which both ^{diamond bonds (bonds by sp 3} hybrid orbitals between carbons) and graphite bonds ( ^{bonds by sp 2 hybrid orbitals between carbons) are mixed.} .. Diamond-like carbon may contain atoms other than carbon atoms (for example, hydrogen atom, oxygen atom, silicon atom, nitrogen atom, aluminum atom, boron atom, phosphorus atom). The silicon oxide layer is preferably a silicon oxide layer formed by vapor deposition.

(Functional layer)
The functional layer is disposed on the substrate. The functional layer is composed of an intermediate layer and a surface layer directly laminated on the intermediate layer. The surface layer is a functional layer that plays a role of imparting specific performance to the base material. The intermediate layer is a layer that plays a role in suppressing deterioration of the performance of the surface layer over time and improving the durability of the functional layer in the functional layer. The performance imparted to the base material by the functional layer is not particularly limited, and includes antifouling property, chemical resistance, abrasion resistance, weather resistance, hydrophilicity, water repellency, oil repellency, etc., and constitutes the surface layer. It is appropriately selected depending on the compound to be used.

In the present invention, the boundary between the surface layer and the intermediate layer of the functional layer is a point where the C content is 5 atomic% or less by the analysis of the C content in the depth direction, that is, the thickness direction of the functional layer as described above. It is defined by (starting point S). In the functional layer according to the present invention, the Al content in the surface layer region of the intermediate layer is 55 atomic% or more and 98 atomic% or less in a predetermined depth region from the starting point S.

Specifically, the C content and the Al content in the present invention are determined as follows by X-ray photoelectron spectroscopy (XPS).
<Device>
X-ray photoelectron spectroscopy analyzer; Quantera-SXM manufactured by ULVAC-PHI
<Measurement conditions>
X-ray source; monochromatic AlKα ray with a beam diameter of about 100 μmφ Photoelectron detection angle; 45 degree pass energy; 224 eV
Spatter ion; Ar ion with acceleration voltage of 1 kV

<Method>
_{First, using a SiO 2} film (standard sample) having a known film thickness on a silicon wafer, the raster size of the sputter gun is adjusted so that the sputtering rate of the _{SiO 2 film is 1.00 nm / min or less.}

Next, under the above sputtering conditions, the depth profile of the integrated intensity of the peaks of C1s, O1s, Al2p, and Si2p is acquired from the air side of the functional layer. At this time, the sputtering interval is 1 minute. From the integrated intensity of each peak, the C content and Al content are calculated using the analysis software attached to the device. The Al content in the surface layer region of the intermediate layer is the average value of two or more measurement points included in the region Q of the depth direction profile, and the depth of the functional layer from the outermost surface on the air side is the standard sample. From the sputter rate obtained in the analysis, it is obtained as a SiO ₂ conversion value.

(Middle layer)
The intermediate layer contains silicon oxide and aluminum oxide. The intermediate layer may contain components other than silicon oxide and aluminum oxide in a total amount of less than 5 atomic% with respect to all the constituent materials of the intermediate layer. In the present invention, the intermediate layer preferably contains substantially no components other than silicon oxide and aluminum oxide. In addition, in this specification, "substantially not contained" means that it is not positively contained, but it is allowed to be mixed by unavoidable impurities.

The intermediate layer has a C content of 5 atomic% or less, and contains Al in a region of 1.0 nm or more and 3.0 nm or less in the depth direction from the interface between the surface layer and the intermediate layer, that is, the surface layer region of the intermediate layer. The rate is 55 atomic% or more and 98 atomic% or less.

When the Al content in the surface layer region of the intermediate layer is 55 atomic% or more, the effect of improving the durability of the functional layer by laminating the intermediate layer can be obtained. The Al content in the surface layer region of the intermediate layer is preferably 65 atomic% or more, more preferably 75 atomic% or more. Further, the Al content in the surface layer region of the intermediate layer is 98 atomic% or less from the viewpoint of having high hardness, and 97 atomic% or less is more preferable, and 95 atoms% or less from the viewpoint of the effect of improving the durability of the functional layer. % Or less is particularly preferable. That is, the Al content in the surface layer region of the intermediate layer is 55 atomic% or more and 98 atomic% or less, preferably 65 atomic% or more and 97 atomic% or less, and particularly preferably 75 atomic% or more and 95 atomic% or less.

In the intermediate layer, at least the Al content in the surface layer region of the intermediate layer may be within the above range, and the Al content other than the surface layer region of the intermediate layer may not be in the above range. The Al content other than the surface layer region of the intermediate layer is an average value of the Al content in the depth range (2 nm) other than the surface layer region of the intermediate layer. However, from the viewpoint of hardness and durability of the functional layer, it is preferable that the Al content other than the surface layer region of the intermediate layer is also within or close to the above range. That is, the content ratio of silicon oxide and aluminum oxide in the intermediate layer is preferably a ratio such that the Al content is within or close to the above range as an average value in the depth range (2 nm).

The thickness of the intermediate layer is preferably 3 to 200 nm, more preferably 4 to 150 nm, and particularly preferably 5 to 100 nm. When the thickness of the intermediate layer is 3 nm or more, the effect of improving the durability of the surface layer by installing the intermediate layer can be sufficiently obtained. When the thickness of the intermediate layer is 200 nm or less, the wear resistance of the intermediate layer itself becomes high. In this specification, the thickness of the intermediate layer is defined as the _{SiO 2} conversion value obtained by the above-mentioned X-ray photoelectron spectroscopy.

(Surface layer)
The surface layer in the present invention is formed using an organic compound having a group capable of reacting with silicon oxide and aluminum oxide. During the formation of the surface layer, at least a part of the groups capable of reacting with the silicon oxide and aluminum oxide of the compound at the interface between the surface layer and the intermediate layer reacts with the silicon oxide and aluminum oxide of the intermediate layer to form a condensate. Form. In this way, at the interface between the surface layer and the intermediate layer, the above compound and the silicon oxide and aluminum oxide in the intermediate layer interact with each other, so that the article with the functional layer of the present invention has excellent durability. ..

Examples of the group capable of reacting with silicon oxide and aluminum oxide include a group having a hydroxyl group and a group capable of generating a hydroxyl group (for example, a group in which the hydroxyl group is protected by an arbitrary protecting group). Among them, one or more selected from silanol groups and hydrolyzable silyl groups are preferable from the viewpoint of reactivity with silicon oxide and aluminum oxide, and hydrolyzable silyl groups are preferable from the viewpoint of storage stability of the compound.

When the group capable of reacting with silicon oxide and aluminum oxide in the above compound is a hydrolyzable silyl group, the hydrolyzable silyl group in the above compound (for example, -SiR _n L _{3-n in the formula 1 described later)} ) Hydrolyzes to form a silanol group (Si-OH). The obtained silanol groups undergo a condensation reaction between the molecules to form a Si—O—Si bond, or the silanol groups in the compound react with the silanol groups (Si—OH) or Al—OH groups in the intermediate layer. It is considered that a bond (Si—O—Si bond or Al—O—Si bond) is formed. That is, the surface layer in this case contains a condensate obtained by hydrolyzing and condensing a compound having a hydrolyzable silyl group. The surface layer may consist only of a condensate of a compound having a hydrolyzable silyl group, or may contain an unreacted product of a compound having a hydrolyzable silyl group. As described below, the unreacted material can be removed as needed.

The thickness of the surface layer is preferably 0.1 to 100 nm, and particularly preferably 0.1 to 50 nm. When the thickness of the surface layer is 0.1 nm or more, the effect of the surface treatment can be sufficiently obtained. When the thickness of the surface layer is 100 nm or less, the utilization efficiency is high. In this specification, the thickness of the surface layer is defined as the _{SiO 2} conversion value obtained by the above-mentioned X-ray photoelectron spectroscopy.

(Compound having a hydrolyzable silyl group)
The compound having a hydrolyzable silyl group may be a fluorine-containing compound having a hydrolyzable silyl group (hereinafter, also simply referred to as “fluorine-containing compound”) from the viewpoint of obtaining a surface layer having water-repellent and oil-repellent properties. preferable.

Among the compounds having a hydrolyzable silyl group, the compounds having no fluorine atom include an organosilane compound having a hydrolyzable silyl group, a silane compound having a polydimethylsiloxane chain structure (neither of them has a fluorine atom), and the like. Can be mentioned.

The number of hydrolyzable silyl groups in the compound having a hydrolyzable silyl group is preferably two or more, and particularly preferably three or more, from the viewpoint of further excellent wear resistance of the surface layer. The upper limit is not particularly limited, but from the viewpoint of ease of production, 15 pieces are preferable, and 12 pieces are particularly preferable.

Examples of the fluorine-containing compound include a fluorine-containing compound having a fluoroalkyl group and a fluorine-containing compound having an ether oxygen atom between carbon atoms of the fluoroalkyl group, such as water repellency, oil repellency, fingerprint stain removing property, and lubricity. A fluorine-containing compound having a perfluoroalkyl group and a fluorine-containing compound having an ethereal oxygen atom between carbon atoms of the perfluoroalkyl group are preferable from the viewpoint of being able to form an excellent surface layer.

Further, as the fluorine-containing compound, a fluorine-containing compound having a poly (oxyfluoroalkylene) chain is preferable because a surface layer having excellent water and oil repellency, fingerprint stain removing property, lubricity and the like can be formed, and poly (oxyperfluoro) is preferable. A fluorine-containing compound having an alkylene) chain is more preferable.

In particular, as the fluorine-containing compound, a fluorine-containing compound having a fluoroalkyl group and a poly (oxyfluoroalkylene) chain (hereinafter referred to as “fluorine-containing compound”) can form a surface layer having excellent water and oil repellency, fingerprint stain removing property, lubricity and the like. It is also referred to as “fluorine-containing ether compound”).

As the fluoroalkyl group, a fluoroalkyl group having 1 to 10 carbon atoms is preferable, a fluoroalkyl group having 1 to 6 carbon atoms is more preferable, and a fluoroalkyl group having 1 to 3 carbon atoms is particularly preferable, from the viewpoint of excellent water and oil repellency. .. Further, the fluoroalkyl group may be linear or branched, preferably linear. Further, the fluoroalkyl group is preferably a perfluoroalkyl group from the viewpoint of being more excellent in physical properties of the surface layer.

Examples of the fluorine-containing compound having a perfluoroalkyl group and a hydrolyzable silyl group include compounds represented by the formula (3) in paragraphs [0010] and [0022] of JP-A-2009-139530. Be done.

The poly (oxyfluoroalkylene) chain is preferably composed of an oxyfluoroalkylene group having 1 to 10 carbon atoms, and particularly preferably one composed of an oxyperfluoroalkylene group having 1 to 10 carbon atoms. From the viewpoint of further excellent abrasion resistance and fingerprint stain removing property of the surface layer, those composed of a plurality of oxyperfluoroalkylene groups having 1 to 10 carbon atoms are preferable.

For example, it is composed of a plurality of oxyperfluoroalkylene groups having 1 carbon atom and a plurality of oxyperfluoroalkylene groups having 2 carbon atoms, a plurality of oxyperfluoroalkylene groups having 1 carbon atom, and a plurality of oxyperfluoroalkylene groups having 3 carbon atoms. It consists of a plurality of oxyperfluoroalkylene groups having 2 carbon atoms and a plurality of oxyperfluoroalkylene groups having 3 carbon atoms, and a plurality of oxyperfluoroalkylene groups having 2 carbon atoms and a plurality of oxyperfluoroalkylene groups having 4 carbon atoms. It consists of a plurality of oxyperfluoroalkylene groups having 1 carbon atom and a plurality of oxyperfluoroalkylene groups having 5 carbon atoms, and a plurality of oxyperfluoroalkylene groups having 1 carbon atom and a plurality of oxyperfluoroalkylene groups having 6 carbon atoms. Those consisting of a plurality of at least three or more kinds of oxyperfluoroalkylene groups selected from 1 to 4 carbon atoms can be mentioned.

The arrangement of the plurality of oxyperfluoroalkylene groups may be block, random, or alternating. When the oxyperfluoroalkylene group has 2 or more carbon atoms, it is preferably a linear oxyperfluoroalkylene group.

The poly (oxyperfluoroalkylene) chain includes a linear oxyperfluoroalkylene group having 1 carbon atom and a linear oxyperfluoroalkylene group having 2 carbon atoms arranged at random, and a linear oxy of 1 carbon acid. A perfluoroalkylene group and a linear oxyperfluoroalkylene group having 3 carbon atoms are randomly arranged, and a linear oxyperfluoroalkylene group having 2 carbon atoms and a linear oxyperfluoroalkylene group having 4 carbon atoms alternate. Those arranged in are particularly preferable.

When the fluorine-containing compound is a fluorine-containing ether compound, the fluorine-containing ether compound preferably has two or more hydrolyzable silyl groups from the viewpoint of interaction between the surface layer and the intermediate layer.
The number average molecular weight of the fluorine-containing ether compound is preferably 500 to 20,000, more preferably 800 to 10,000, and particularly preferably 1,000 to 8,000 from the viewpoint of abrasion resistance of the surface layer.

As the fluorine-containing ether compound, compound 1 is preferable because the surface layer has more excellent water and oil repellency.
[A-O-Z ^1- (R ^f O) _m- ] _j Z ² [-SiR _n L _3-n ] _q Equation 1

A is a perfluoroalkyl group or −Q [−SiR _n L _3-n ] _k .
The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3 from the viewpoint of more excellent abrasion resistance of the surface layer.
The perfluoroalkyl group may be linear or branched.
However, when A is −Q [−SiR _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 ) −, etc., and CF 3} −, CF ₃ CF ₂ −, CF ₃ CF ₂ from the viewpoint of superior water and oil repellency of the surface layer. CF ₂ -is preferable.

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 excluding _{SiR n} L _3-n from formulas 2-1 and 2-2 and formulas 2-1 to 2-1-6, which will be described later. Can be mentioned.

R is a monovalent hydrocarbon group.
R is particularly preferably a monovalent saturated hydrocarbon group. 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 becomes a silanol group by the hydrolysis reaction. The silanol groups further react between the silanol groups to form a Si—O—Si bond.

Examples of L include an alkoxy group, a halogen atom, an acyl group, an isocyanate group (-NCO) and the like. As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom, a chlorine atom is preferable.
As L, an alkoxy group or a halogen atom having 1 to 4 carbon atoms is preferable from the viewpoint of easy industrial production. As L, an alkoxy group having 1 to 4 carbon atoms is preferable, and an ethoxy group is particularly preferable when long-term storage stability of the compound is required, because there is little outgassing during coating and the storage stability of the compound is more excellent. Preferably, a methoxy group is particularly preferable when the reaction time after coating is short.

n is an integer of 0 to 2.
n is preferably 0 or 1, and 0 is particularly preferable. The presence of a plurality of L makes the interaction between the surface layer and the intermediate layer good, and the durability of the functional layer of the present invention is excellent.
When n is 1 or less, the plurality of Ls present in one molecule may be the same or different from each other. From the viewpoint of availability of raw materials and ease of production, they are preferably the same.

Hydrolyzable silyl groups (SiR _n L _3-n ) include -Si (OCH ₃ ) ₃ , -SiCH ₃ (OCH ₃ ) ₂ , -Si (OCH ₂ CH ₃ ) ₃ , -SiCl ₃ , -Si ( OC (O) CH ₃ ) ₃ and −Si (NCO) ₃ are preferable. _{-Si (OCH 3} ) ₃ is particularly preferable from the viewpoint of ease of handling in industrial manufacturing.

Z ¹ is a single bond, an oxyfluoroalkylene group having 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced with a fluorine atom (however, the oxyperfluoroalkylene group is excluded. The oxygen atom in the oxyfluoroalkylene group is , (R ^f O) _m ), or a poly (oxyfluoroalkylene) group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms (bonded to ^{(R f} O) _m). oxygen atoms in the oxy-fluoroalkylene group is (R f ^O) binds to _m. oxyfluoroalkylene group bonded to (R f ^O) _m is. poly (oxy-fluoroalkylene comprising one or more hydrogen atoms The group may contain both an oxyperfluoroalkylene group in which all hydrogen atoms are substituted with fluorine atoms and an oxyfluoroalkylene group containing one or more hydrogen atoms.) The oxyfluoroalkylene group or poly (oxyfluoroalkylene) group preferably has 1 to 10 carbon atoms.

Z ¹ _{has a single bond, -CHFCF 2} OCH ₂ CF ₂ O-, -CF ₂ CHFCF ₂ OCH ₂ CF ₂ CF ₂ O-, -CF ₂ CF ₂ CHFCF ₂ OCH ₂ CF because it is easy to produce a compound. ₂ O-, -CF ₂ CF ₂ OCHFCF ₂ OCH ₂ CF ₂ O-, -CF ₂ CF ₂ OCF ₂ CF ₂ OCHFCF ₂ OCH ₂ CF ₂ O-, -CF ₂ CH ₂ OCH ₂ CF ₂ O-, -CF ₂ CF ₂ OCF ₂ CH ₂ OCH ₂ CF ₂ O- is preferable (however, the left side binds to A-O), and single bond, -CHFCF ₂ OCH ₂ CF ₂ O- is particularly preferable.

R ^f is a perfluoroalkylene group.
The number of carbon atoms of the perfluoroalkylene group is preferably 1 to 6 from the viewpoint of more excellent water and oil repellency of the surface layer.
The perfluoroalkylene group may be linear or branched, but is preferably linear because it is more excellent in water and oil repellency of the surface layer.
The plurality of R ^fs may be the same or different. That is, (R ^f O) _m may be composed of two or more types of R ^{f O having different carbon atoms.}

m is an integer of 2 to 200, preferably an integer of 5 to 150, and particularly preferably an integer of 10 to 100. When m is 2 or more, the water and oil repellency of the surface layer is more excellent. When m is 200 or less, the durability of the surface layer is more excellent.

In (R ^f O) _m , when two or more kinds of R ^f O having different carbon atoms are present, ^{the bonding order of each R f} O is not limited. For example, when two types of R ^f O are present, the two types of R ^f O may be randomly, alternately, or arranged in blocks.

As (R ^f O) _m , {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 (CF ₂ CF ₂ CF ₂ O) _m13 (CF _{2 O) m13 (CF 2 O) m11 (CF 2 CF 2 O) m12 (CF 2 CF 2 CF 2 O) m13 (CF 2 O) m} CF ₂ CF ₂ CF ₂ O) _m14 }, (CF ₂ CF ₂ O) _m16, (CF ₂ CF ₂ CF ₂ O) _m17 , (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _m15 ( CF ₂ CF ₂ O), (CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _m18 (CF ₂ O), (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _m19 (CF ₂ CF ₂ O), {(CF ₂ O) _m20 (CF ₂ CF ₂ CF ₂ O) _m21 }, {(CF ₂ CF ₂ O) _m22 (CF ₂ CF ₂ CF ₂ O) _m23 } Is preferable, and {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 (CF ₂ CF ₂ CF ₂ O) _m13 (CF ₂ CF ₂ CF ₂ CF ₂ O) _m14 }, (CF ₂ CF ₂ O-CF) ₂ CF ₂ CF ₂ CF ₂ O) _m15 (CF ₂ CF ₂ O), (CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _m18 (CF ₂ O), (CF ₂ CF ₂ O-CF) ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _m19 (CF ₂ CF ₂ O) is particularly preferable.

However, m11 and m12, each an integer of 1 or more, m13 and m14 are each 0 or an integer of 1 or more, m11 + m12 + m13 + m14 is an integer of 2 to 200, m11 amino _CF 2 O, m12 amino The bonding order of CF ₂ CF ₂ O, m13 CF ₂ CF ₂ CF ₂ O, and m14 CF ₂ CF ₂ CF ₂ CF ₂ O is not limited. m16 and m17 are integers of 2 to 200, respectively, and m15 and m18 to m23 are integers of 1 to 99, respectively.

Z ² is a (j + q) -valued linking group.
Z ² 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 excluding _{SiR n} L _3-n from formulas 2-1 and 2-2 and formulas 2-1 to 2-1-6, which will be described later. Can be mentioned.

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 surface layer, and 1 is particularly preferable from the viewpoint of easy production of a compound.
q is an integer of 1 or more, and is preferably an integer of 2 or more, more preferably an integer of 2 to 4, particularly preferably 2 or 3, and even more preferably 3 because the surface layer is more excellent in water and oil repellency. ..

Compound 1 is preferably compound 1-1 because the surface layer has more excellent water and oil repellency.
A-O-Z ^1- (R ^f O) _m- Z ³ formula 1-1
The definitions of A, Z ¹ , R ^f and m in Formula 1-1 are synonymous with the definitions of each group in Formula 1.

Z ³ is a group 2-1 or a group 2-2.
−R ^f7 −Q ^a −X (−Q ^b −SiR _n L _3-n ) _h (−R ⁷ ) _i equation 2-1
−R ^f7 −Q ⁷¹ − [CH ₂ C (R ⁷¹ ) ( ^{−Q 72} −SiR _n L _3-n )] _y −R ⁷² Equation 2-2

In formulas 2-1 and 2-2, the definitions of R, L and n are synonymous with the definitions of each group in formula 1.

R ^f7 is a perfluoroalkylene group.
The number of carbon atoms of the perfluoroalkylene group is preferably 1 to 30, and particularly preferably 1 to 6.
The perfluoroalkylene group may be linear or branched.
The R ^f7, from the viewpoint of easily producing the _{compound, -CF 2 CF 2 CF 2 CF} 2 - or _{-CF 2 CF 2 CF 2 CF 2} CF 2 - is preferred.

Q ^a is a single bond or divalent linking group.
The divalent linking group may be, for example, a divalent hydrocarbon group (a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, an alkenylene group, or an alkynylene group. Divalent saturated hydrocarbon group. The hydrogen group may be linear, branched or cyclic, and examples thereof include an alkylene group. The carbon number is preferably 1 to 20, and the divalent aromatic hydrocarbon group has a carbon number of carbon. 5 to 20 is preferable, and examples thereof include a phenylene group. In addition, an alkenylene group having 2 to 20 carbon atoms and an alkynylene group having 2 to 20 carbon atoms may be used.) A divalent heterocyclic group. , -O-, -S-, -SO _2- , -N (R ^d )-, -C (O)-, -Si ( ^Ra ) _2-, and a group combining two or more of these. .. Here, ^Ra is an alkyl group (preferably 1 to 10 carbon atoms) or a phenyl group. R ^d is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
Examples of the group in which two or more of these are combined include -OC (O)-, -C (O) N (R ^d )-, an alkylene group-O-alkylene group, and an alkylene group -OC (O). -Alkylene group, alkylene group-Si ( ^Ra ) ₂ -phenylene group-Si ( ^Ra ) ₂ can be mentioned.

X is a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom or a 2-8 valent organopolysiloxane residue.
The alkylene group may have —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group. The alkylene group may have a plurality of groups selected from the group consisting of -O-, a silphenylene skeleton group, a divalent organopolysiloxane residue and a dialkylsilylene group.
The alkylene group represented by X preferably has 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
Examples of the 2 to 8 valent organopolysiloxane residue include a divalent organopolysiloxane residue and a (w + 1) -valent organopolysiloxane residue described later.

Q ^b is a single bond or divalent linking group.
Definition of the divalent linking group are the same as those defined as described in the above-described Q ^a.

R ⁷ is a hydroxyl group or an alkyl group.
The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1.

When X is a single bond or an alkylene group, h is 1 and i is 0.
When X is a nitrogen atom, h is an integer of 1 to 2, i is an integer of 0 to 1, and h + i = 2 is satisfied.
When X is a carbon atom or a silicon atom, h is an integer of 1 to 3, i is an integer of 0 to 2, and h + i = 3 is satisfied.
When X is a 2 to 8 valent organopolysiloxane residue, h is an integer of 1 to 7, i is an integer of 0 to 6, and h + i = 1 to 7 is satisfied.
If ^{_{(-Q b -SiR n L 3-}} n) is two or more, two or more ^{_{(-Q b -SiR n L 3-}} n) may be be the same or different. If R ⁷ is two or more, two or more (-R ⁷⁾ may be be the same or different.

^Q71 is a single bond, an alkylene group, or a group having an ethereal oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms, and a single bond is preferable from the viewpoint of easy production of a compound.
The alkylene group preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
The carbon number of the group having an ethereal oxygen atom between the carbon atoms of the alkylene group having 2 or more carbon atoms is preferably 2 to 10, and particularly preferably 2 to 6.

R ⁷¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a hydrogen atom is preferable from the viewpoint of easy production of a compound.
As the alkyl group, a methyl group is preferable.

Q ⁷² is a single bond or an alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms. ^{Q 72} is preferably a single bond or −CH ₂₋ from the viewpoint of easy production of a compound.

R ⁷² is a hydrogen atom or a halogen atom, and a hydrogen atom is preferable because it is easy to produce a compound.

y is an integer of 1 to 10, and an integer of 1 to 6 is preferable.
Two or more [CH ₂ C (R ⁷¹ ) (-Q ^72- SiR _n L _3-n )] may be the same or different.

The group 2-1 is preferably groups 2-1 to 2-1-6.
−R ^f7 − (X ¹ ) _p −Q ¹ −SiR _n L _3-n Equation 2-1-1
−R ^f7 − (X ² ) _r −Q ²¹ −N [−Q ²² −SiR _n L _3-n ] ₂ equations 2-1-2
−R ^f7 −Q ³¹ −G (R ³ ) [ ^{−Q 32-} SiR _n L _3-n ] ₂ equations 2-1-3
−R ^f7 − [C (O) N (R ^d )] _s −Q ⁴¹ − (O) _t −C [− (O) _u −Q ⁴² −SiR _n L _3-n ] ₃ equation 2-1-4
−R ^f7 −Q ⁵¹ −Si [−Q ⁵² −SiR _n L _3-n ] ₃ formula 2-1-5
−R ^f7 − [C (O) N (R ^d )] _v −Q ⁶¹ −Z ³ [−Q ⁶² −SiR _n L _3-n ] _w Equation 2-1-6
^{The definitions of R f7} , R, L, and n in the formulas 2-1 to 2-1-6 are as described above.

X ¹ is -O- or -C (O) N (R ^d )-(where N in the equation is bound to ^{Q 1).}
The definition of R ^d is as described above.
p is 0 or 1.

Q ¹ is an alkylene group. The alkylene group may have —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group. The alkylene group may have a plurality of groups selected from the group consisting of -O-, a silphenylene skeleton group, a divalent organopolysiloxane residue and a dialkylsilylene group.
When the alkylene group has an —O—, silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group, it is preferable to have these groups between carbon atoms.

The alkylene group represented by Q ¹ is 1 to 10 preferably 2 to 6 is particularly preferred.

As for Q ¹ , when p is 0, −CH ₂ OCH ₂ CH ₂ CH ₂ −, −CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ −, −CH ₂ CH ₂ −, −CH ₂ CH ₂ CH ₂ −, −CH ₂ OCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ − is preferable. (X ¹ ) When _p is −O−, −CH ₂ CH ₂ CH ₂ − and −CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ − are preferable. (X ¹ ) When _p is −C (O) N (R ^d ) −, an alkylene group having 2 to 6 carbon atoms is preferable (however, N in the formula is bonded to ^{Q 1).} If Q ¹ is these groups, the compound can be easily produced.

Specific examples of the group 2-1-1 include the following groups.

X ² is -O-, -NH-, or -C (O) N (R ^d )-.
The definition of R ^d is as described above.

Q ²¹ is a single bond, an alkylene group, or an ethereal oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms, −C (O) −, −C (O) O−, −OC ( O) A group having − or −NH−.
The alkylene group represented by Q ²¹ is 1 to 10 preferably 2 to 6 is particularly preferred.
Carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ²¹ - etheric oxygen atom between carbon atoms, -C (O) -, - C (O) O -, - OC (O) - or -NH The number of carbon atoms of the group having − is preferably 2 to 10, and particularly preferably 2 to 6.

The Q ^21, from the viewpoint of easily producing the _{compound, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 OCH 2 CH 2 -, - CH 2 NHCH 2 CH 2 -, -CH ₂ CH ₂ OC (OCH ₂ CH _2- is preferable (however, the right side binds to N).

r is 0 or 1 ( ^{where 0 if Q 21} is a single bond). 0 is preferable from the viewpoint that the compound can be easily produced.

Q ²² represents an alkylene group or a carbon atom number of 2 or more alkylene group having a carbon - between carbon atoms, a divalent organopolysiloxane residues, etheric oxygen atom or a group having -NH-.
The alkylene group represented by Q ²² is 1 to 10 preferably 2 to 6 is particularly preferred.
Carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ²² - between carbon atoms, a divalent organopolysiloxane residues, the number of carbon atoms of the group having an etheric oxygen atom or -NH- is 2-10 Is preferable, and 2 to 6 are particularly preferable.

The Q ^22, from the viewpoint of easily producing the _{compound, -CH 2 CH 2 CH 2 -} , - CH 2 CH 2 OCH 2 CH 2 CH 2 - is preferred (but the right side is attached to the Si.).

The two [-Q ^22- SiR _n L _3-n ] may be the same or different.

Specific examples of the group 2-1-2 include the following groups.

Q ³¹ is a single bond, an alkylene group, or a group having an ethereal oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms, and a single bond is preferable from the viewpoint of easy production of a compound.
The alkylene group represented by Q ³¹ is 1 to 10 preferably 2 to 6 is particularly preferred.
Carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ³¹ - number of carbon atoms of the group having an etheric oxygen atom between carbon atoms, preferably 2 to 10, 2 to 6 is particularly preferred.

G is a carbon atom or a silicon atom.
R ⁶ is a hydroxyl group or an alkyl group. The number of carbon atoms of the alkyl group represented by ^{R 3 is preferably 1 to 4.}
As G (R ³ ), C (OH) or Si (R ^3a ) (however, R ^3a is an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 10 and methyl The group is particularly preferable.) Is preferable.

Q ³² 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.
The alkylene group represented by Q ³² is 1 to 10 preferably 2 to 6 is particularly preferred.
Carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ³² - number of carbon atoms of the group having an etheric oxygen atom or a divalent organopolysiloxane residues between the carbon atoms is preferably 2 to 10, 2 6 is particularly preferable.
As Q ³² _{, −CH 2} CH ₂ −, −CH ₂ CH ₂ CH ₂ −, −CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ − are preferable from the viewpoint of easy production of a compound.
The two [-Q ^32- SiR _n L _3-n ] may be the same or different.

Specific examples of groups 2-1-3 include the following groups.

The definition of R ^{d in} Equation 2-1-4 is as described above.
s is 0 or 1.
Q ⁴¹ represents a single bond, an alkylene group or a carbon atom of the alkylene group having 2 or more carbon atoms - a group having an etheric oxygen atom between carbon atoms.
The alkylene group represented by Q ⁴¹ is 1 to 10 preferably 2 to 6 is particularly preferred.
Carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁴¹ - number of carbon atoms of the group having an etheric oxygen atom between carbon atoms, preferably 2 to 10, 2 to 6 is particularly preferred.
t is 0 or 1 (however, 0 when Q ⁴¹ is a single bond).
As for −Q ⁴¹ − (O) _t −, when s is 0, it is a single bond, −CH ₂ O− _{, −CH 2} OCH ₂ −, −CH ₂ OCH ₂ CH _{2 because it is easy to produce a compound.} O−, −CH ₂ OCH ₂ CH ₂ OCH ₂ −, −CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ − is preferable (however, the left side ^{binds to R f7} ), and when s is 1, single _{bond, -CH 2 -, - CH 2} CH 2 - is preferred.

Q ⁴² is an alkylene group, the alkylene group -O -, - C (O) N (R d) - [in ^{R d} definitions are as described above. ], It may have a silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group.
When the alkylene group has an —O— or sylphenylene skeletal group, it is preferable to have an —O— or sylphenylene skeletal group between carbon atoms. When the alkylene group has a -C (O) N (R ^d )-, dialkylsilylene group or a divalent organopolysiloxane residue, it is between carbon atoms or the end on the side that binds to _{(O) u1.} It is preferable to have these groups in.
The alkylene group represented by Q ⁴² is 1 to 10 preferably 2 to 6 is particularly preferred.

u is 0 or 1.
- _(O) u ^{-Q 42} - as it is from the viewpoint of easily producing the _{compound, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - CH 2 OCH 2 CH 2 CH 2 -, - CH 2 OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ −, −OCH ₂ CH ₂ CH ₂ −, −OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ −, −OSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ −, −CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ PhSi (CH ₃ ) ₂ CH ₂ CH ₂ − is preferable (however, the right side is bonded to Si).

The three [-(O) _u- Q ^42- SiR _n L _3-n ] may be the same or different.

Specific examples of groups 2-1-4 include the following groups.

Q ⁵¹ represents an alkylene group, or a carbon atom of the alkylene group having 2 or more carbon atoms - a group having an etheric oxygen atom between carbon atoms.
The alkylene group represented by Q ⁵¹ is 1 to 10 preferably 2 to 6 is particularly preferred.
Carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁵¹ - number of carbon atoms of the group having an etheric oxygen atom between carbon atoms, preferably 2 to 10, 2 to 6 is particularly preferred.
The Q ^51, from the viewpoint of easily producing the _{compound, -CH 2 OCH 2 CH 2 CH} 2 -, - CH 2 OCH 2 CH 2 OCH 2 CH 2 CH 2 -, - CH 2 CH 2 -, - CH 2 CH ₂ CH ₂ -is preferable (however, the right side is bonded to Si).

Q ⁵² 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.
The carbon number of the alkylene group represented by Q ⁵² is preferably 1 to 10, and particularly preferably 2 to 6.
Carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁵² - number of carbon atoms of the group having an etheric oxygen atom or a divalent organopolysiloxane residues between the carbon atoms is preferably 2 to 10, 2 6 is particularly preferable.
The Q ^52, from the viewpoint of easily producing the _{compound, -CH 2 CH 2 CH 2 -} , - CH 2 CH 2 OCH 2 CH 2 CH 2 - is preferred (but the right side is attached to the _{SiR n L 3-n} .).

The three [-Q ^52- SiR _n L _3-n ] may be the same or different.

Specific examples of groups 2-1-5 include the following groups.

The definition of R ^{d in} Equation 2-1-6 is as described above.
v is 0 or 1.

Q ⁶¹ represents an alkylene group, or a carbon atom of the alkylene group having 2 or more carbon atoms - a group having an etheric oxygen atom between carbon atoms.
The alkylene group represented by Q ⁶¹ is 1 to 10 preferably 2 to 6 is particularly preferred.
Carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁶¹ - number of carbon atoms of the group having an etheric oxygen atom between carbon atoms, preferably 2 to 10, 2 to 6 is particularly preferred.
The Q ^61, from the viewpoint of easily producing the _{compound, -CH 2 OCH 2 CH 2 CH} 2 -, - CH 2 OCH 2 CH 2 OCH 2 CH 2 CH 2 -, - CH 2 CH 2 -, - CH 2 CH ₂ CH ₂ − is preferred (however, the right side binds to ^{Z 3).}

Z ³ is a (w + 1) -valent organopolysiloxane residue.
w is an integer of 2 to 7.
Examples of the (w + 1) -valent organopolysiloxane residue include the following groups. ^{However, Ra} in the following equation is as described above.

Q ⁶² 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.
The alkylene group represented by Q ⁶² is 1 to 10 preferably 2 to 6 is particularly preferred.
Carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁶² - number of carbon atoms of the group having an etheric oxygen atom or a divalent organopolysiloxane residues between the carbon atoms is preferably 2 to 10, 2 6 is particularly preferable.
The Q ^62, from the viewpoint of easily producing the _{compound, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 - is preferred.

The w [-Q ^62- SiR _n L _3-n ] may be the same or different.

Specific examples of Compound 1 include International Publication No. 2013/042732, International Publication No. 2013/121984, International Publication No. 2013/121985, International Publication No. 2013/121986, International Publication No. 2014/163004, International Publication No. Fluorine-containing ether compounds described in JP-A-2015 / 087902, JP-A-2014-080473 and JP-A-2015-199906, perfluoro (poly) ether-containing silane compounds described in Patent Document 1, and Patent Document 2. Fluoroxyalkylene group-containing polymer, the compound described in Patent Document 3, and the like can be mentioned.

As the fluorine-containing ether compound, a commercially available product can also be used. For example, KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Industry Co., Ltd., Optool (registered trademark) DSX, Optool (registered trademark) AES, Optool (registered trademark) manufactured by Daikin Industries, Ltd. Examples thereof include UF503, Optool (registered trademark) UD509, and Afluid (registered trademark) S550 manufactured by Asahi Glass Co., Ltd.

The article with a functional layer of the present invention is an article with a functional layer having excellent durability, in which the deterioration of the performance of the surface layer with time is suppressed by having the intermediate layer. For example, when the surface layer has water repellency and oil repellency, the water contact angle can be mentioned as an index for measuring water repellency. The water contact angle of the surface of the surface layer on the air side is preferably 100 degrees or more, more preferably 105 degrees or more, further preferably 110 degrees or more, and particularly preferably 115 degrees or more. When the water contact angle is 100 degrees or more, the water repellency of the surface layer is excellent. Since the higher the water contact angle of the surface layer is, the more preferable it is, the upper limit is not particularly limited. The water contact angle is measured using a contact angle measuring device (DM-500: product name, manufactured by Kyowa Interface Science Co., Ltd.).

The article with a functional layer of the present invention uses, for example, a reciprocating traverse tester (manufactured by Daiei Seiki Co., Ltd.) for the air-side surface of the surface layer in accordance with JIS L0849: 2013 (ISO 105-X12: 2001). It is preferable that the water contact angle can be maintained at 100 degrees or more after the steel wool bonster (count: # 0000, dimensions: 5 mm × 10 mm × 10 mm) is reciprocated 3,000 times at a load of 9.8 N and a speed of 80 rpm. It is more preferable that the temperature can be held at 105 degrees or higher.

In the article with a functional layer of the present invention, for example, for the air-side surface of the surface layer, the value obtained by subtracting the water contact angle of the surface layer after the above 3,000 round trips from the initial water contact angle (contact angle reduction amount) is obtained. , 25 degrees or less, more preferably 15 degrees or less, and particularly preferably 10 degrees or less. Since the smaller the contact angle reduction amount is, the more preferable it is, the lower limit value is not particularly limited.

The article with a functional layer of the present invention is assumed to have excellent durability because it has a high hardness measured on the air side surface of the surface layer, for example, a Martens hardness. In the article with a functional layer of the present invention, the indentation test device (Picodenter HM500 manufactured by Fisher) was used for the air-side surface of the surface layer, the pushing load was 0.03 mN, the holding time was 5 seconds, the load speed and the unloading were performed. The Martens hardness measured at a speed of 0.05 mN / 5 seconds is preferably 8,500 MPa or more, more preferably 10,000 MPa or more.

[Manufacturing method of goods with functional layer]
As a method for producing an article with a functional layer of the present invention, a method of forming the intermediate layer and forming a surface layer on the surface of the intermediate layer using an organic compound having a group capable of reacting with silicon oxide and aluminum oxide is used. Can be mentioned.

(Formation of intermediate layer)
The method for forming the intermediate layer is not particularly limited, and examples thereof include dry coating and wet coating. Dry coating is preferable because the Al content in the surface layer region of the intermediate layer can be easily adjusted and the hardness of the layer can be increased.

Examples of the dry coating include a physical vapor deposition method (vacuum vapor deposition method, ion plating method, sputtering method), a chemical vapor deposition method (thermal CVD method, plasma CVD method, optical CVD method), ion beam sputtering method and the like.

When the intermediate layer is formed by dry coating, the vacuum deposition method or the sputtering method is preferable, and the sputtering method is particularly preferable because a functional layer having good reactivity with the surface layer and excellent durability can be formed.

Specific methods for forming the intermediate layer by the vacuum vapor deposition method include a method of co-depositing silicon oxide and aluminum oxide to form the intermediate layer, and a method of forming a mixture of silicon oxide and aluminum oxide by vapor deposition. Can be mentioned.

The temperature at the time of vacuum deposition is preferably 20 to 300 ° C, particularly preferably 30 to 200 ° C. The pressure during vacuum deposition ^{is preferably 1 × 10 -1} Pa or less, and particularly preferably 1 × 10 ^{-2 Pa or less.}

Specific methods for forming the intermediate layer by the sputtering method include a method of selecting a sputtering target and an atmospheric gas according to the constituent materials and performing sputtering by a conventional method. In the intermediate layer in the present invention, for example, a SiAl mixed target in which the atomic% of Al is 55 to 98 atomic% with respect to the total amount of silicon atoms (Si) and aluminum atoms (Al) is used, and the oxidizing gas concentration is sufficiently adjusted. A film can be formed by performing reactive sputtering in a high sputter gas. As the sputtering gas in this case, a mixed gas of Ar and oxygen is preferably used.

Further, by using two types of targets, a target made of Si alone and a target made of Al alone, and changing the input power for each target, the content ratio of Si and Al in the obtained intermediate layer can be adjusted. You may. In this case as well, the intermediate layer can be formed by performing reactive sputtering in a sputtering gas having a sufficiently high oxidizing gas concentration.

Further, first, using a SiAl mixed target in which the atomic% of Al is 55 to 98 atomic% with respect to the total amount of Si and Al, sputtering is performed in an inert gas such as Ar gas, and an intermediate layer composed of only Si and Al is performed. The precursor layer may be formed, and then, for example, a radio frequency (RF) plasma may be used to react the precursor layer with oxygen to form an intermediate layer.

Also in this method, a precursor layer may be formed by using two types of a target composed of Si alone and a target composed of Al alone, and then an oxidation reaction may be carried out.

Wet coatings include sol-gel method, 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 method. , The gravure coat method and the like.

When the intermediate layer is formed by a wet coating, it is preferably formed from a mixture of silicon alkoxide and aluminum alkoxide (or aluminum alkoxide) by the sol-gel method.

(Formation of surface layer)
After forming the intermediate layer, the surface layer is formed by wet coating or dry coating an organic compound having a group capable of reacting with silicon oxide and aluminum oxide.

Examples of the dry coating include the same method as in the case of the intermediate layer described above. In an organic compound having a group capable of reacting with silicon oxide and aluminum oxide, when the group is a hydrolyzable silyl group, the compound The vacuum vapor deposition method is particularly preferable from the viewpoint of suppressing decomposition and the simplicity of the apparatus. At the time of vacuum vapor deposition, a metal porous body such as iron or steel was impregnated with an organic compound having a group capable of reacting with silicon oxide and aluminum oxide or a composition containing the same, or a solution or dispersion in which a solvent was added thereto. Pellets may be used.

The temperature at the time of vacuum deposition is preferably 20 to 300 ° C, particularly preferably 30 to 200 ° C. The pressure during vacuum deposition ^{is preferably 1 × 10 -1} Pa or less, and particularly preferably 1 × 10 ^{-2 Pa or less.}

In the dry coating, one of the organic compounds having a group capable of reacting with silicon oxide and aluminum oxide may be used alone, or a mixture of two or more kinds of organic compounds having a group capable of reacting with silicon oxide and aluminum oxide. It may be used as a composition containing an organic compound having a group capable of reacting with silicon oxide and aluminum oxide and other components (excluding the solvent), and a solution obtained by adding a solvent to these. Alternatively, it may be used as a dispersion.

As the wet coating, the same method as in the case of the intermediate layer described above can be mentioned. In wet coating, a coating liquid for forming a surface layer is preferably used. The coating liquid for forming a surface layer is a solution or a dispersion liquid containing an organic compound having a group capable of reacting with silicon oxide and aluminum oxide and a solvent.

The solvent is appropriately selected depending on the type of the organic compound having a group capable of reacting with silicon oxide and aluminum oxide. When the compound is a fluorine-containing compound, an organic solvent is preferable as the solvent. The organic solvent may be a fluorine-based organic solvent, a non-fluorine-based organic solvent, or both solvents. Examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols and the like.

As the non-fluorine-based organic solvent, a compound consisting of only hydrogen atoms and carbon atoms and a compound consisting of only hydrogen atoms, carbon atoms and oxygen atoms are preferable, and hydrocarbon-based organic solvents, alcohol-based organic solvents, ketone-based organic solvents, etc. Examples thereof include ether-based organic solvents and ester-based organic solvents.

The coating liquid for forming the surface layer contains not only organic compounds and solvents having a group capable of reacting with silicon oxide and aluminum oxide, but also other components and impurities (hydrolyzable silyl groups) as long as the effects of the present invention are not impaired. It may contain a by-product produced in the manufacturing process of the compound having the compound). As other components, for example, in an organic compound having a group capable of reacting with silicon oxide and aluminum oxide, when the group is a hydrolyzable silyl group, the hydrolysis and condensation reaction of the hydrolyzable silyl group is promoted. Examples thereof include known additives such as an acid catalyst and a basic catalyst.

The solid content concentration of the coating liquid for forming the surface layer is preferably 0.001 to 50% by mass, particularly preferably 0.05 to 30% by mass. The solid content concentration of the surface layer forming coating liquid is a value calculated from the mass of the surface layer forming coating liquid before heating and the mass after heating in a convection dryer at 120 ° C. for 4 hours.

<Post-processing>
In order to improve the wear resistance of the surface layer, if necessary, an operation for accelerating the reaction between the organic compound having a group capable of reacting with silicon oxide and aluminum oxide and the intermediate layer may be carried out. Examples of the operation include heating, humidification, and light irradiation. For example, in an organic compound having a group capable of reacting with silicon oxide and aluminum oxide, when the group is a hydrolyzable silyl group, a base material with an intermediate layer having a surface layer formed in the atmosphere having water may be used. When heated, it has a hydrolyzable silyl group such as a hydrolyzable silyl group to a silanol group, a silanol group condensation reaction to form a siloxane bond, a silanol group on the surface of the intermediate layer, an Al-OH group, etc. Reactions such as a condensation reaction of a compound with a silanol group can be promoted.

After the surface treatment, the compounds in the surface layer that are not chemically bonded to other compounds or the intermediate layer may be removed if necessary. Specific methods include, for example, a method of pouring a solvent over the surface layer, a method of wiping with a cloth soaked with the solvent, and the like.

[Use]
The article with a functional layer of the present invention is preferably used for an article for transportation equipment, an article for precision equipment, an article for optical equipment, an article for construction, or an article for electronic equipment. Further, the article with the functional layer of the present invention may be used for articles other than the above-mentioned various devices.

Specific examples of articles for transportation equipment include exterior members, interior members, glass (for example, windshield, side glass and rear glass), mirrors, tire wheels, etc. in trains, automobiles, ships, aircraft, and the like. Specific examples of articles for precision equipment include window materials in photographic equipment. Specific examples of articles for optical instruments include lenses. Specific examples of building articles include windows, floor materials, wall materials, and door materials. Specific examples of articles for electronic devices include display glass, display protective films, antireflection films, and fingerprint sensors in communication terminals or image display devices.

According to the present invention, an intermediate layer containing silicon oxide and aluminum oxide is formed on the surface of the base material, and an organic compound having a group capable of reacting with silicon oxide and aluminum oxide is wet-coated or dried on the intermediate layer. A method of forming a surface layer by coating to obtain an article with a functional layer having a functional layer including the intermediate layer and the surface layer directly laminated on the intermediate layer, wherein X in the functional layer At each depth point of the depth profile obtained by photoelectron spectroscopy, the ratio of carbon atoms to the total number of carbon atoms, oxygen atoms, aluminum atoms, and silicon atoms became 5 atomic% or less for the first time. The average value in the depth direction of the ratio of aluminum atoms to the total number of silicon atoms and aluminum atoms in the region of 1.0 nm or more and 3.0 nm or less in the depth direction from the above starting point is 55 atom%. Provided is a method for producing an article with a functional layer having a content of 98 atomic% or less.
The description of each configuration in the above manufacturing method is the same as described above, and thus will be omitted.

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. Examples 1 to 3 are examples, and examples 4 to 7 are comparative examples.

In each example, the following materials were used to produce articles with a functional layer having water and oil repellency as performance, and the following physical property measurements and evaluations were performed.
[material]
Base material: Sapphire substrate (100 mmφ, thickness 0.8 mm, manufactured by Shinko Co., Ltd.)
An organic compound having a group capable of reacting with silicon oxide and aluminum oxide; a fluorine-containing ether compound represented by the following chemical formula synthesized by the method for synthesizing the compound (ii-2) in WO2014 / 126064 (number average molecular weight: 4). , 920) (hereinafter referred to as "fluorine-containing ether compound F").
CF ₃ CF ₂ OCF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ CF ₂ OCF ₂ CF ₂ O) ₁₃ CF ₂ CF ₂ CF ₂ C (O) NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

[Physical characteristics and evaluation]
(C content and Al content)
The C content and Al content were calculated by the following devices, measurement conditions, and methods. The measurement was performed once for each.

<Device>
X-ray photoelectron spectroscopy analyzer; Quantera-SXM manufactured by ULVAC-PHI
<Measurement conditions>
X-ray source; monochromatic AlKα ray with a beam diameter of about 100 μmφ Photoelectron detection angle; 45 degree pass energy; 224 eV
Step energy; 0.4 eV / step
Spatter ion; Ar ion X-ray beam irradiation diameter with acceleration voltage of 1 kV; 100 μmφ
Measurement area: 100 μmφ
Sputter gun ion species; Ar ⁺
Acceleration voltage of spatter gun; 1kV
Raster size of spatter gun; 3 x 3 mm ²
Sputtering interval; 1 minute SiO ₂ equivalent sputtering rate on silicon wafer of sputter gun; 0.78 nm / min

<Method>
_{First, using a SiO 2} film having a known film thickness on a silicon wafer (standard sample, a thermal oxide film manufactured by _{KST World), the sputter rate of the SiO 2} film is 1.00 nm / min or less. As described above, the raster size of the spatter gun was adjusted to ^{3 × 3 mm 2.} The sputtering rate of the SiO ₂ film at a raster size of 3 × 3 mm ² was 0.78 nm / min.

Next, under the above sputtering conditions, a depth profile of the integrated intensities of the peaks of C1s, O1s, Al2p, and Si2p was obtained from the air side of the functional layer. At this time, the sputtering interval was set to 1 minute increments. From the integrated intensity of each peak, the C content and Al content were calculated using the analysis software (MultiPak Version 9.3.0.3) attached to the device. The Al content in the surface layer region of the intermediate layer is an average value of two points in the depth direction included in the region Q. The depth of the functional layer from the outermost surface on the air side was determined as _{a SiO 2 conversion value from the sputtering rate obtained in the analysis of the standard sample.}

(Initial water contact angle)
The contact angle when 2 μL of distilled water was dropped onto the air-side surface of the surface layer was measured at 20 ° C. using a contact angle measuring device (DM-701 manufactured by Kyowa Interface Science Co., Ltd.). Measurements were performed at five different locations on the surface of the surface layer, and the average value was calculated.

(Martens hardness)
For the surface of the surface layer, using an indentation test device (Picodenter HM500 manufactured by Fisher), the indentation load was 0.03 mN, the holding time was 5 seconds, and the load speed and unloading speed were 0.05 mN / 5 seconds. Unit: MPa) was measured. Measurements were performed at three different points on the surface of the surface layer, and the average value was calculated.

(Steel wool wear test)
For the surface layer, a steel wool bonster (count: # 0000, dimensions: 5 mm x 10 mm x) was used using a reciprocating traverse tester (manufactured by Daiei Seiki Co., Ltd.) 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 3,000 round trips, the water contact angle of the surface layer was measured and evaluated according to the following criteria.

A; Water contact angle of the surface layer after 3,000 round trips is 105 degrees or more B; Water contact angle of the surface layer after 3,000 round trips is 100 degrees or more and less than 105 degrees C; After 3,000 round trips The water contact angle of the surface layer is less than 100 degrees

Further, the value obtained by subtracting the water contact angle of the surface layer after 3,000 round trips from the initial water contact angle was defined as the amount of decrease in the contact angle. The larger the water contact angle after wear and the smaller the decrease in water contact angle due to wear (the amount of decrease in contact angle), the smaller the decrease in performance due to wear and the better the durability.

[Examples 1 to 5]
(Cleaning of base material (removal of impurities))
The sapphire substrate was washed by immersing it in an alkaline aqueous solution (Shikaclean LX-IV; product name, manufactured by Kanto Chemical Co., Inc., concentration 10% by mass), and further washed with ion-exchanged water.

(Formation of intermediate layer)
After the metal sputtering described in Japanese Patent Application Laid-Open No. 2007-248562, a load-lock type sputtering device (RAS-1100BII, manufactured by Syncron) was used on one main surface of the cleaned sapphire substrate. An intermediate layer, which is a mixed film of aluminum oxide and silicon oxide, was formed by an oxidation reaction) to obtain a sapphire substrate with an intermediate layer. The sputtering apparatus includes two film forming chambers and one reaction chamber equipped with an RF plasma source. A polycrystalline silicon target was placed in the film forming chamber 1, and a pure aluminum target was placed in the film forming chamber 2. The sapphire substrate was fixed to the film forming holder, and the load lock chamber was evacuated. After introducing the substrate holder into the film forming chamber through the load lock chamber, the film ^{forming was started after the film forming chamber became 2.0 × 10 -4} Pa or less.

In the film formation, the film formation holder was rotated at 60 pm, and the sapphire substrate was conveyed in the order of the film formation chamber 1, the film formation chamber 2, and the reaction chamber, so that Si sputtering, Al sputtering, and oxidation reaction were performed in this order. .. In each example, the process gas shown in Table 1 was introduced into the film forming chamber 1, the film forming chamber 2, and the reaction chamber at the flow rates shown in Table 1, respectively. Table 1 shows the amounts of power input to the sputtering cathodes of the film forming chamber 1 and the film forming chamber 2 and the RF plasma source of the reaction chamber in each example. Further, the substrate temperature and the film formation rate are also shown in Table 1.

In Table 1, 5N and 4N in parentheses after the target indicate purity. Specifically, 5N is 99.999999% and 4N is 99.99999%.

(Surface layer film formation)
0.5 g of fluorine-containing ether compound F was placed as a vapor deposition source on a molybdenum boat in a vacuum vapor deposition apparatus (VTR-350M, manufactured by ULVAC Kiko Co., Ltd.). The sapphire substrate with the intermediate layer obtained above 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 300 ° C., and a fluorine-containing ether compound F was vacuum-deposited on the intermediate layer to form a thin-film deposition film. The sapphire substrate with an intermediate layer on which the vapor-deposited film was formed was heated (post-treated) at a temperature of 200 ° C. for 30 minutes to obtain an article with a functional layer.

[Example 6]
_{Silicon oxide (manufactured by Canon Optron, SiO 2} (C)) was placed as a vapor deposition source on a molybdenum boat in a vacuum vapor deposition apparatus (manufactured by ULVAC, Inc., VTR-350M). A sapphire substrate washed in the same manner as in Example 1 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 1,000 ° C. and silicon oxide was vacuum-deposited to form a thin-film deposition film.

Further, a surface layer was formed on the intermediate layer of the obtained sapphire substrate with an intermediate layer in the same manner as in Example 1 to obtain an article with a functional layer.

[Example 7]
In the same manner as in Example 1, a surface layer was formed on one main surface of the washed sapphire substrate in the same manner as in Example 1 to obtain an article with a functional layer.

For the articles with functional layers obtained in each of the above examples, the Al content [atomic%] in the surface layer region of the intermediate layer was determined by the above method. In addition, the articles with functional layers obtained in each of the above examples were evaluated by the above methods, such as measurement of initial water contact angle, measurement of maltens hardness, and steel wool wear test. The results are shown in Table 1.

Further, the starting point S of the article with the functional layer obtained in each of the above examples was a point 0.8 nm in the depth direction from the outermost surface of the article with the functional layer. That is, the thickness of the surface layer obtained by the above-mentioned X-ray photoelectron spectroscopy was 0.8 nm in terms of _{SiO 2.} The thickness of the intermediate layer determined by the above-mentioned X-ray photoelectron spectroscopy was 23.0 to 28.0 nm in terms of _{SiO 2.}

As is clear from Table 1, the articles with the functional layer obtained in Examples 1 to 3 of the examples of the present invention have a high initial contact angle, and the water contact angle after the steel wool wear test is also obtained. The high level can be maintained.

The article with a functional layer of the present invention is an article with a functional layer having a functional layer composed of an intermediate layer and a surface layer on a base material, and is durable because the deterioration of the performance of the surface layer with time is suppressed. Excellent for. The article with a functional layer of the present invention having such characteristics is preferably used for an article for transportation equipment, an article for precision equipment, an article for optical equipment, an article for construction, or an article for electronic equipment. Further, the article with the functional layer of the present invention may be used for articles other than the above-mentioned various devices.

10 ... Article with functional layer, 1 ... Base material, 2 ... Intermediate layer, 3 ... Surface layer, 4 ... Functional layer

Claims (5)

With the base material
An article with a functional layer having a functional layer laminated on a base material.
The functional layer includes an intermediate layer containing silicon oxide and aluminum oxide, and a surface layer formed by using an organic compound having a group capable of reacting with silicon oxide and aluminum oxide, which is directly laminated on the intermediate layer. Consists of
At each depth point of the depth profile obtained by X-ray photoelectron spectroscopy in the functional layer, the ratio of carbon atoms to the total number of carbon atoms, oxygen atoms, aluminum atoms, and silicon atoms is 5 atomic% or less for the first time. The average of the ratio of aluminum atoms to the total number of silicon atoms and aluminum atoms in the region of 1.0 nm or more and 3.0 nm or less in the depth direction from the starting point. An article with a functional layer, characterized in that the value is 55 atomic% or more and 98 atomic% or less. The article with a functional layer according to claim 1, wherein the organic compound contains a fluorine-containing compound. The article with a functional layer according to claim 2, wherein the fluorine-containing compound has a poly (oxyperfluoroalkylene) chain. The article with a functional layer according to any one of claims 1 to 3, wherein the base material is sapphire. An intermediate layer containing silicon oxide and aluminum oxide is formed on the surface of the base material to form an intermediate layer.
A surface layer is formed by wet-coating or dry-coating an organic compound having a group capable of reacting with silicon oxide and aluminum oxide on the intermediate layer.
A method for obtaining an article with a functional layer having the intermediate layer and a functional layer including the surface layer directly laminated on the intermediate layer.
At each depth point of the depth profile obtained by X-ray photoelectron spectroscopy in the functional layer, the ratio of carbon atoms to the total number of carbon atoms, oxygen atoms, aluminum atoms, and silicon atoms is 5 atomic% or less for the first time. The average of the ratio of aluminum atoms to the total number of silicon atoms and aluminum atoms in the region of 1.0 nm or more and 3.0 nm or less in the depth direction from the starting point. A method for producing an article with a functional layer, wherein the value is 55 atomic% or more and 98 atomic% or less.

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