WO2019124269A1 - Article equipped with functional layer and method for manufacturing article equipped with functional layer - Google Patents

Abstract

Provided is an article equipped with a functional layer, in which the decrease in performance of the functional layer over time is minimized, whereby an excellent durability is obtained. An article equipped with a functional layer, having a substrate and a functional layer laminated on the substrate, wherein: the functional layer comprises an intermediate layer containing silicon oxide and aluminum oxide, and a surface layer, which is directly laminated on the intermediate layer and which is formed using an organic compound having a group capable of reacting with silicon oxide and aluminum oxide; and when the depth point, from among the depth points of a depth-direction profile acquired by X-ray photoelectron spectroscopy in the functional layer, at which the proportion of C atoms relative to the total number of C, O, Al, and Si atoms first reaches 5 atom% is deemed to be the origin, the average value of the proportion of Al atoms relative to the total number of Si and Al atoms in a region of 1.0 to 3.0 nm in the depth direction from the origin is 55 to 98 atom%.

Description

Article with functional layer and method of manufacturing article with functional layer

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 substrates, there is known a technique of providing a layer having desired performance on the substrate. As a method of forming the layer, a method is known in which a compound having a target performance and having a group capable of reacting with a substrate is reacted with the substrate.

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

Japanese Patent Publication No. 2016-500030

However, although the articles obtained by using the known techniques by the present inventors have good film forming properties of the layer and sufficient performance can be obtained in the initial state, it is attributed to the durability of the layer while in use. It was found that the performance was lost.

This invention is made from the said viewpoint, Comprising: It makes it a subject to provide the articles | goods with a functional layer which are excellent in durability by the time-dependent fall of the performance of a functional layer being suppressed.

The present invention provides an article with a functional layer and a method for producing an article with a functional layer having the following configuration.
[1] An article with a functional layer comprising a substrate and a functional layer laminated on the substrate, wherein the functional layer is an interlayer comprising silicon oxide and aluminum oxide, and directly on the interlayer And a surface layer formed by using an organic compound having a group capable of reacting with silicon oxide and aluminum oxide, which is laminated, and X-ray photoelectron spectroscopy using ion sputtering 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 is 5 atomic% or less for the first time at each depth point of the acquired depth direction profile, The average value of the ratio of aluminum atoms to the total number of silicon atoms and aluminum atoms in the region of 1.0 to 3.0 nm in the depth direction from the origin is Characterized in that it is a 55 to 98 atomic%, functional layers with articles.
[2] The article of [1], wherein the organic compound is a fluorine-containing compound.
[3] The article of [2], wherein the fluorine-containing compound is a compound having a poly (oxyperfluoroalkylene) chain.
[4] The article according to any one of [1] to [3], wherein the organic compound is an organic compound having one or more groups selected from a silanol group and a hydrolyzable silyl group.
[5] The article according to any one of [1] to [4], wherein the thickness of the intermediate layer calculated from the depth direction profile obtained by the X-ray photoelectron spectroscopy is 3 to 200 nm.
[6] The article according to any one of [1] to [5], wherein the substrate is made of sapphire.

[7] Forming an interlayer comprising silicon oxide and aluminum oxide on the surface of a substrate, and wet-coating or dry-coating an organic compound having silicon oxide and a group capable of reacting with aluminum oxide on the interlayer. A surface layer is formed by the following method to obtain an article with a functional layer, which has a functional layer including the intermediate layer and the surface layer directly laminated on the intermediate layer,
The ratio of carbon atoms to the total number of carbon atoms, oxygen atoms, aluminum atoms, and silicon atoms at each depth point in the depth direction profile obtained by X-ray photoelectron spectroscopy using ion sputtering in the functional layer is The average value of the ratio of aluminum atoms to the total number of silicon atoms and aluminum atoms in the region from 1.0 to 3.0 nm in the depth direction starting from the depth point where the first reduction to 5 atomic% or less Is 55 to 98 atomic%, and the method for producing an article with a functional layer.
[8] The production method of [7], wherein the intermediate layer is formed by wet coating.
[9] The production method of [7], wherein the intermediate layer is formed by dry coating.
[10] The method of [9], wherein the dry coating is a sputtering method.

ADVANTAGE OF THE INVENTION According to this invention, the articles | goods with a functional layer which are excellent in durability can be provided by the time-dependent fall of the performance of a functional layer being suppressed.

It is a sectional view showing the article with a functional layer roughly.

In the present specification, the compound represented by the formula (1) is referred to as a compound (1). The compounds represented by other formulas are similarly described. The group represented by the formula (1) is referred to as a group (1). The same applies to groups represented by other formulas.
In the present specification, when "the alkylene group may have an A group", the alkylene group may have an A group between carbon atom and carbon atom in the alkylene group, and an alkylene group It may have an A group at the end like -A group-.

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 hydrolysis reaction. For example, -SiR _n L _3-n in formula (1).
The term "etheric oxygen atom" means an oxygen atom that forms an ether bond (-O-) between carbon and carbon atoms. The chemical formula of the oxyperfluoroalkylene group is represented by the oxygen atom thereof described on the right side of the perfluoroalkylene group.

The "divalent organopolysiloxane residue" is a group represented by the following formula. R ^a in the following formula is an alkyl group (preferably having a carbon number of 1 to 10) or a phenyl group. Further, g1 is an integer of 1 or more, preferably an integer of 1 to 9, and particularly preferably an integer of 1 to 4.

The “silphenylene skeleton group” is a group represented by —Si (R ^b ) ₂ PhSi (R ^b ) ₂ — (wherein Ph is a phenylene group and R ^b is a monovalent organic group). It is. As R ^b , an alkyl group (preferably having a carbon number of 1 to 10) is preferable.
The “dialkylsilylene group” is a group represented by —Si (R ^c ) ₂ — in which R ^c is an alkyl group (preferably having a carbon number of 1 to 10).
The "number average molecular weight" of the fluorine-containing ether compound is calculated by determining the number (average value) of oxyperfluoroalkylene groups based on the terminal group by ¹ H-NMR and ¹⁹ F-NMR using NMR analysis. Be done.

[Articles with Functional Layer]
The article with a functional layer of the present invention has a substrate and a functional layer laminated on the substrate.
The functional layer in the present invention comprises an intermediate layer laminated on a substrate and a surface layer laminated directly on the intermediate layer. That is, among the two layers constituting the functional layer, the intermediate layer is present on the substrate side, and the surface layer is present on the air side. The intermediate layer contains silicon oxide and aluminum oxide, and the surface layer is formed using an organic compound having silicon oxide and a group capable of reacting with aluminum oxide. Hereinafter, an organic compound having a group capable of reacting with silicon oxide and aluminum oxide is also referred to as a reactive group-containing organic compound.
The “functional layer laminated on the substrate” is not limited to the case where the layer is laminated directly on the substrate, but also includes the case where another layer is provided between the substrate and the functional layer, The configuration of is the same.

The functional layer in the present invention is a carbon atom, carbon atoms, oxygen atoms, aluminum atoms, and carbon atoms relative to the total number of silicon atoms at each depth point in the depth direction profile obtained by X-ray photoelectron spectroscopy using ion sputtering. A region with a depth of 5 atomic% or less for the first time is a starting point (hereinafter, also referred to as “starting point S”), and a region of 1.0 to 3.0 nm in the depth direction from the starting point S (hereinafter, “region The average value of the ratio of aluminum atoms to the total number of silicon atoms and aluminum atoms in Q) is also 55 to 98 atomic%.
The depth of the horizontal axis of the profile in the depth direction obtained by X-ray photoelectron spectroscopy is the sputter rate of the SiO ₂ film determined using a thermal oxide film (SiO ₂ film) with a known film thickness on a silicon wafer. It is a converted value. In addition, it is necessary to adjust the sputtering rate of ion sputtering to be 1.00 nm / min or less as the sputtering rate of the SiO ₂ film.

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

In the functional layer, as described above, the surface layer is a layer mainly composed of an organic substance, and the intermediate layer is a layer containing an inorganic substance. Therefore, if the C content at each point set at predetermined intervals in the depth direction from the outermost surface of the surface layer side of the functional layer is measured, the C content maintaining a predetermined value in the region of the surface layer is greatly reduced It is possible to recognize the point where the carbon content rate is 5 atomic% or less (starting point S) as the boundary between the surface layer surface 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, it is possible to regard the surface from the outermost surface on the air side of the functional layer to the starting point S as the surface layer, and the starting point S to the interface between the functional layer and the base as the intermediate layer. Therefore, the region Q is rephrased as a region of 1.0 to 3.0 nm deep in the thickness direction from the interface with the surface layer in the intermediate layer (hereinafter, also referred to as “the surface region of the intermediate layer”). In the following description, the average value of the Al content in the region Q is referred to as “the Al content in the surface layer region of the intermediate layer”.

Furthermore, the thickness of the intermediate layer is preferably 3 to 200 nm. The thickness of the intermediate layer can be defined as the depth from the starting point S in the depth direction profile obtained by X-ray photoelectron spectroscopy using ion sputtering to the interface (end point E) between the intermediate layer and the base material.

The article with a functional layer of the present invention has the above-described configuration, so that the temporal deterioration of the performance of the functional layer is suppressed, and the article is excellent in durability. The reason for this is not necessarily clear, but 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 substrate. Furthermore, when the Al content in the surface layer region of the intermediate layer is within the predetermined range, the hardness of the intermediate layer and the interaction between the intermediate layer and the surface layer are balanced, so the durability of the functional layer is improved. , It is considered that the performance of the functional layer is highly maintained.

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. An article 10 with a functional layer according to an embodiment of the present invention shown in FIG. 1 has a plate-like base 1 and a functional layer 4 laminated on one main surface 1 a of the base 1. The functional layer 4 has the intermediate layer 2 on the base 1 side, and has the surface layer 3 on the main surface 2 a opposite to the surface of the intermediate layer 2 in contact with the base 1.

As shown in FIG. 1, the article 10 with a functional layer may have the functional layer 4 only on one main surface 1 a of the substrate 1 and further has the functional layer 4 on the other main surface 1 b or side surface May be Moreover, when it has the functional layer 4 only in one main surface 1a of the base material 1, you may have the functional layer 4 on the whole surface, and you may have the functional layer 4 in one part. In the functional layer 4, the surface layer 3 may not completely cover the intermediate layer 2. The location where the functional layer 4 is provided is suitably adjusted according to the use of the article with a functional layer.

In the configuration of the functional layer-containing article 10, if necessary, the main surface 1b of the base 1 opposite to the functional layer 4 is not impaired by the effects of the present invention between the base 1 and the functional layer 4. Additional layers may be provided. When an additional layer is provided, the interface between the intermediate layer and the additional layer is an end point E.

(Base material)
The base material in the present invention is not particularly limited as long as it is a base material for which surface modification (impartation of specific performance) is required. The material of the substrate includes metal, resin, glass (which may be chemically strengthened), sapphire, ceramic, stone, and a composite material of these. Among these, sapphire is preferable in that the effects of the present invention are more remarkably exhibited.

The substrate may have a single layer structure or a laminated structure. In the substrate, it is preferable that at least the main surface on which the intermediate layer is formed be made of sapphire. Generally, sapphire means α-Al ₂ O ₃ . In the present specification, α-Al ₂ O ₃ crystals containing minor components (eg, 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 substrate are not particularly limited. It selects suitably according to the use of the article with a functional layer mentioned below.

In order to further improve the adhesion between the substrate and the functional layer, the surface of the substrate may be subjected to an activation treatment (for example, a dry activation treatment, a wet activation treatment). Specific examples of dry activation treatment include treatment of irradiating the surface of a substrate with active energy rays (for example, ultraviolet rays, electron beams, X-rays), corona discharge treatment, vacuum plasma treatment, atmospheric pressure plasma treatment, flame treatment , Itro treatment. Specific examples of the wet activation treatment include treatment of bringing the surface layer into contact with an acid or alkaline solution. Among the above-mentioned activation treatments, corona discharge treatment is preferable in terms of further improving the adhesion between the substrate and the intermediate layer.

Moreover, you may use as a base material what has a further layer on the surface of the base material body which consists of a material mentioned above. The layer may be any layer other than the functional layer of the present invention and the layers (intermediate layer and surface layer) possessed by the functional layer of the present invention, but from the point of being excellent in the effect of the present invention A layer excellent in the above is preferred, and specific examples include a diamond like carbon layer and a silicon oxide layer.

A diamond-like carbon layer means a film having an amorphous structure in which both a diamond bond (a bond between carbons by sp ³ hybrid orbitals) and a graphite bond (a bond by carbons sp ² hybrid orbitals) are mixed. . Diamond-like carbon may contain atoms other than carbon atoms (for example, hydrogen atoms, oxygen atoms, silicon atoms, nitrogen atoms, aluminum atoms, boron atoms, phosphorus atoms). 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 layer that plays a role in providing the substrate with specific performance in the functional layer. The intermediate layer is a layer that plays a role in suppressing deterioration in performance of the surface layer with the passage of time and improving the durability of the functional layer in the functional layer. The performance imparted to the substrate by the functional layer is not particularly limited, and examples thereof include soil resistance, chemical resistance, abrasion resistance, weather resistance, hydrophilicity, water repellency, oil repellency, etc., and constitute the surface layer. Is appropriately selected depending on the compound to be

In the present invention, the boundary between the surface layer of the functional layer and the intermediate layer is the point at which the C content is 5 atomic% or less by the analysis of the C content in the depth direction of the functional layer, ie, the thickness direction as described above. (Starting point S). In the functional layer according to the present invention, in the predetermined depth region from the starting point S, the Al content in the surface region of the intermediate layer is 55 to 98 atomic%.
The thickness of the intermediate layer is the depth from the start point S to the end point E as described above.

Specifically, the C content, the Al content, and the thickness of the intermediate layer in the present invention are determined by X-ray photoelectron spectroscopy (XPS) as follows.
<Device>
X-ray photoelectron spectrometer; Quantera-SXM manufactured by ULVAC-PHI
<Measurement conditions>
X-ray source; monochromatized AlK α ray with a beam diameter of about 100 μm, photoelectron detection angle: 45 degrees, path energy; 224 eV
Sputtering ion; Ar ion with acceleration voltage 1 kV

<Method>
First, using a thermal oxide film (SiO ₂ film) with a known film thickness on a silicon wafer as a standard sample, adjust the raster size of the sputtering gun so that the sputtering rate of the SiO ₂ film is 1.00 nm / min or less. Do.

Then, under the above-mentioned sputtering conditions, C1s, O1s, Al2p, Si2p from the air side of the functional layer, and, if necessary, a further layer provided between the base immediately below the intermediate layer or the base and the functional layer Acquire the depth direction profile of the integrated intensity of the characteristic peak of the element. At this time, the sputtering interval is set to one minute. From the integrated intensity of each peak, the C content and the Al content are calculated using 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 from the outermost surface on the air side of the functional layer is the above standard sample From the sputter rate obtained in the analysis, it is determined as a SiO ₂ conversion value.
The way of determining the end point E is appropriately changed depending on the substrate immediately below the intermediate layer or the additional layer provided between the substrate and the functional layer.

When the additional layer provided between the base immediately below the intermediate layer or between the base and the functional layer is an oxide, first, the ratio of Si atomic concentration to O atomic concentration (Si / O atomic concentration ratio) is taken as the vertical axis And create a depth direction profile. Next, the difference between the Si / O atomic concentration ratio at a given depth point A and the point B plotted next to the point A viewed from the air side of the functional layer is taken as the ΔSi / O atomic concentration ratio. And a depth profile is created with the ΔSi / O atomic concentration ratio as the vertical axis. The end point E is determined from among the extreme points found in the depth direction profile with the ΔSi / O atomic concentration ratio as the vertical axis.
When the additional layer provided between the base immediately below the intermediate layer or between the base and the functional layer mainly comprises only Si atoms, the ratio of Al atomic concentration to Si atomic concentration (Al / Si atomic concentration ratio) An axial depth profile is created, and an end point E is determined from among extreme points found in the depth profile, the vertical axis of which is the ΔAl / Si atomic concentration ratio created in the same procedure as described above.
When the additional layer provided between the base immediately below the intermediate layer or between the base and the functional layer is not composed only of oxide or mainly Si atoms, the base immediately below the intermediate layer or the base and the functional layer Create a depth direction profile with the ratio of Si atomic concentration to atomic concentration of element (element X) that is the main component of the further layer provided between (Si / element X atomic concentration ratio) as the vertical axis, The end point E is determined from among the extreme points recognized in the depth direction profile with the ΔSi / element X atomic concentration ratio created in the same procedure as the vertical axis.

(Intermediate layer)
The middle layer contains silicon oxide and aluminum oxide. The intermediate layer may contain components other than silicon oxide and aluminum oxide in total 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, it does not contain actively, but not containing it substantially means that the contamination by an unavoidable impurity is accept | permitted.

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

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 the lamination of the intermediate layer can be obtained. 65 atomic% or more is preferable and 70 atomic% or more of Al content rate in the surface layer area | region of an intermediate | middle layer is more preferable. Further, the Al content in the surface layer region of the intermediate layer is 98 atomic% or less from the point of having high hardness, and 97 atomic% or less is more preferable, 90 atomic% or less from the point of the effect of improving the durability of the functional layer. % Or less is particularly preferred. That is, the Al content in the surface layer region of the intermediate layer is 55 to 98 at%, preferably 65 to 97 at%, particularly preferably 70 to 90 at%.

In the intermediate layer, at least the Al content in the surface layer region of the intermediate layer may be in the above range, and the Al content in regions other than the surface layer region of the intermediate layer may not be in the above range. The Al content rate other than the surface layer region of the intermediate layer is an average value of the Al content rate in a depth range (2 nm) other than the surface layer region of the intermediate layer. However, from the viewpoint of the hardness and durability of the functional layer, the Al content other than the surface layer region of the intermediate layer is preferably within the above range. That is, the content ratio of silicon oxide and aluminum oxide in the intermediate layer is preferably such a ratio that the Al content is within 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. If the thickness of the intermediate layer is 3 nm or more, the effect of improving the durability of the surface layer by the provision of the intermediate layer can be sufficiently obtained. If the thickness of the intermediate layer is 200 nm or less, the abrasion resistance of the intermediate layer itself becomes high. In the present specification, the thickness of the intermediate layer is defined as the depth from the start point S to the end point E obtained by the above-mentioned X-ray photoelectron spectroscopy.

(Surface layer)
The surface layer in the present invention is formed using a reactive group-containing organic compound. At the interface between the surface layer and the intermediate layer, at the interface between the surface layer and the intermediate layer, at least a part of the above-mentioned compounds capable of reacting with silicon oxide and aluminum oxide react with silicon oxide and aluminum oxide in the intermediate layer to form a condensate. Form. Thus, the above-mentioned compound interacts with the silicon oxide and aluminum oxide of the intermediate layer at the interface between the surface layer and the intermediate layer, so the article with a functional layer of the present invention is excellent in 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 forming a hydroxyl group (for example, a group in which a hydroxyl group is protected by any protective group). Among them, in view of reactivity with silicon oxide and aluminum oxide, one or more groups selected from a silanol group and a hydrolyzable silyl group are preferable, and from the viewpoint of storage stability of the compound, a hydrolyzable silyl group is preferred. preferable.

In the above compound, when the group capable of reacting with silicon oxide and aluminum oxide is a hydrolyzable silyl group, a hydrolyzable silyl group in the above compound (eg, -SiR _n L ₃ in formula (1) described later) _The hydrolysis reaction of _-n ) forms a silanol group (Si-OH). The resulting silanol group undergoes a condensation reaction between molecules to form a Si-O-Si bond, or the silanol group in the compound reacts with the silanol group (Si-OH) or Al-OH group of the intermediate layer It is believed 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 hydrolytic condensation of 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. If the thickness of the surface layer is 0.1 nm or more, the effect of the surface treatment can be sufficiently obtained. If the thickness of the surface layer is 100 nm or less, the utilization efficiency is high. In the present specification, the thickness of the surface layer is defined as the depth from the surface to the starting point S obtained by the above-mentioned X-ray photoelectron spectroscopy.

(Compound having a hydrolyzable silyl group)
The compound having a hydrolyzable silyl group is a fluorine-containing compound having a hydrolyzable silyl group (hereinafter, also simply referred to as a "fluorine-containing compound") from the viewpoint of obtaining a surface layer having water and oil repellency. preferable.

Among compounds having a hydrolyzable silyl group, compounds having no fluorine atom include organosilane compounds having a hydrolyzable silyl group, silane compounds having a polydimethylsiloxane chain structure (all having no fluorine atom), etc. It can be mentioned.

The hydrolyzable silyl group in the compound having a hydrolyzable silyl group is preferably 2 or more, and more preferably 3 or more, from the viewpoint that the abrasion resistance of the surface layer is further excellent. The upper limit is not particularly limited, but is preferably 15 and more preferably 12 from the viewpoint of ease of production.

Examples of the fluorine-containing compound include fluorine-containing compounds having a fluoroalkyl group, and fluorine-containing compounds further having an etheric oxygen atom between carbon atoms of the fluoroalkyl group, such as water and oil repellency, fingerprint stain removability, lubricity, etc. From the viewpoint of being able to form an excellent surface layer, fluorine-containing compounds having a perfluoroalkyl group and fluorine-containing compounds further having an etheric oxygen atom between carbon atoms of the perfluoroalkyl group are preferable.

Further, as the fluorine-containing compound, a fluorine-containing compound having a poly (oxyfluoroalkylene) chain is preferable because it can form a surface layer excellent in water and oil repellency, fingerprint stain removability, lubricity and the like, and poly (oxyperfluoro fluorocarbon) is preferable. Fluorine-containing compounds having an alkylene) chain are more preferred.

In particular, a fluorine-containing compound having a fluoroalkyl group and a poly (oxyfluoroalkylene) chain (hereinafter referred to as a fluorine-containing compound, from the viewpoint of being able to form a surface layer excellent in water / oil repellency, fingerprint stain removability, lubricity etc. Also referred to as "fluorinated ether compound" is preferred.

The fluoroalkyl group is preferably a fluoroalkyl group having 1 to 10 carbon atoms, more preferably a fluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably 1 to 3 fluoroalkyl group from the viewpoint of excellent water and oil repellency. . The fluoroalkyl group is preferably linear. The fluoroalkyl group is preferably a perfluoroalkyl group from the viewpoint of being more excellent in the 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) described in paragraph [0010] and [0022] of JP-A-2009-139530. Be

As the poly (oxyfluoroalkylene) chain, one comprising an oxyfluoroalkylene group having 1 to 10 carbon atoms is preferable, and one comprising an oxyperfluoroalkylene group having 1 to 10 carbon atoms is particularly preferable. From the viewpoint that the abrasion resistance and the fingerprint stain removability of the surface layer are further excellent, one comprising a plurality of oxyperfluoroalkylene groups having 1 to 10 carbon atoms is preferable.

For example, 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 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 3 carbon atoms, and a plurality of oxyperfluoroalkylene groups having 2 carbon atoms and a plurality of oxyperfluoroalkylene groups having 4 carbon atoms And a plurality of oxyperfluoroalkylene groups having 1 carbon atom and a plurality of oxyperfluoroalkylene groups having 5 carbon atoms, a plurality of oxyperfluoroalkylene groups having 1 carbon atom and a plurality of oxyperfluoroalkylene groups having 6 carbon atoms One, carbon number 1 4 made of a plurality of at least three or more oxyperfluoroalkylene groups selected from and the like.

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

As the poly (oxyperfluoroalkylene) chain, one having a linear oxyperfluoroalkylene group having 1 carbon atom and a linear oxyperfluoroalkylene group having 2 carbon atoms randomly disposed, or a linear oxycarbon 1 having a carbon atom A structure in which a perfluoroalkylene group and a linear oxyperfluoroalkylene group having 3 carbon atoms are randomly disposed, and a linear oxyperfluoroalkylene group having 2 carbon atoms and a linear oxyperfluoroalkylene group having 4 carbon atoms alternate Particularly preferred are those arranged at

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 the 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 the friction resistance of the surface layer.

As a fluorine-containing ether compound, a compound (1) is preferable at the point which the water-oil repellency of a surface layer is more excellent.
[A-O-Z ^1- (R ^f O) _m- ] _j Z ² [-SiR _n L _3-n ] _q (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 20, more preferably 1 to 10, still more preferably 1 to 6, and particularly preferably 1 to 3 because the friction resistance of the surface layer is more excellent.
The perfluoroalkyl group may be linear or branched.
However, j is 1 when A is -Q [-SiR _n L _3-n ] _k .

As a perfluoroalkyl group, 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, from the viewpoint of water and oil repellency of the surface layer is more _{excellent, CF 3 -, CF 3 CF} 2 -, CF 3 CF 2 CF ₂ -is preferred.

Q is a (k + 1) valent linking group. As described later, k is an integer of 1 to 10. Thus, examples of Q include di- to 11-valent linking groups.
Any group may be used as Q as long as it does not impair the effects of the present invention. For example, an alkylene group optionally having an etheric oxygen atom or a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, a silicon atom And a divalent to octavalent organopolysiloxane residue, and SiR _n L from Formula (2-1), Formula (2-2) and Formula (2-1-1) to (2-1-6) described later. Groups other than _3-n can be mentioned.

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

L is a hydrolyzable group or a hydroxyl group.
The hydrolyzable group of L is a group which becomes a hydroxyl group by a hydrolysis reaction. That is, the hydrolyzable silyl group becomes a silanol group by a hydrolysis reaction. The silanol groups further react between silanol groups to form Si-O-Si bonds.

Examples of L include an alkoxy group, a halogen atom, an acyl group and an isocyanate group (—NCO). The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. As a halogen atom, a chlorine atom is preferable.
As L, an alkoxy group having 1 to 4 carbon atoms and a halogen atom are preferable from the viewpoint of easy industrial production. As L, an alkoxy group having 1 to 4 carbon atoms is preferable from the viewpoint of little outgassing at the time of application and the storage stability of the compound being more excellent, and when long-term storage stability of the compound is required, the ethoxy group is particularly Preferably, a methoxy group is particularly preferred when the reaction time after coating is to be short.

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

As the hydrolyzable silyl group (SiR _n L _3-n ), —Si (OCH ₃ ) ₃ , —SiCH ₃ (OCH ₃ ) ₂ , —Si (OCH ₂ CH ₃ ) ₃ , —SiCl ₃ , —Si ( _{OC (O) CH 3) 3} , -Si (NCO) 3 are preferable. -Si (OCH ₃ ) ₃ is particularly preferred from the viewpoint of ease of handling in industrial production.

Z ¹ is a single bond or an oxyfluoroalkylene group having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted by 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 by a fluorine atom (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 ) Groups include both oxyperfluoroalkylene groups in which all hydrogen atoms have been substituted by fluorine atoms, and oxyfluoroalkylene groups containing one or more hydrogen atoms. May be included)). The carbon number of the oxyfluoroalkylene group or the poly (oxyfluoroalkylene) group is preferably 1 to 10.

As Z ¹ , 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 from the viewpoint of easy production of the 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 (but the left side is bonded to A—O), and a single bond, —CHFCF ₂ OCH ₂ CF ₂ O— is particularly preferable.

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

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

When two or more types of R ^f O having different carbon numbers are present in (R ^f O) _m , the bonding order of each R ^f O is not limited. For example, if two R ^f O are present, two R ^f O may be arranged randomly, alternately, in blocks.

^(R f _O) as the _m, from the viewpoint of water and oil repellency of the surface layer is more _{excellent, {(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) _{m 14} }, (CF ₂ CF ₂ O) _{m 16} , (CF ₂ CF ₂ CF ₂ O) _{m 17} , (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _{m 15} ( CF ₂ CF ₂ O), (CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _{m 18} (CF ₂ O), (CF ₂ CF ₂ O-CF ₂ 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 preferred, {( _{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) _{m 15} (CF ₂ CF ₂ O), (CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _{m 18} (CF ₂ O), (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _{m 19} (CF ₂ CF ₂ O) is particularly preferred.

However, m11 and m12 are each an integer of 1 or more, m13 and m14 are each an integer of 0 or 1 and m11 + m12 + m13 + m14 is an integer of 2 to 200, and m11 CF ₂ O, m12 CF ₂ CF ₂ O, bond order of m13 amino _{CF 2 CF 2 CF 2 O,} m14 amino _{CF 2 CF 2 CF 2 CF 2} O is not limited. m16 and m17 are each an integer of 2 to 200, and m15 and m18 to m23 are an integer of 1 to 99.

Z ² is a (j + q) -valent linking group.
Z ² may be any group that does not impair the effects of the present invention, and examples thereof include an alkylene oxygen group optionally having an etheric oxygen atom or a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, and a silicon atom And a divalent to octavalent organopolysiloxane residue, and SiR _n L from Formula (2-1), Formula (2-2) and Formula (2-1-1) to (2-1-6) described later. Groups other than _3-n can be mentioned.

j is an integer of 1 or more, preferably an integer of 1 to 5 from the viewpoint that the water and oil repellency of the surface layer is more excellent, and 1 is particularly preferable from the viewpoint of easy production of the 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 still more preferably 3 because the water and oil repellency of the surface layer is more excellent. .

The compound (1) is preferably the compound (1-1) from the viewpoint that the water and oil repellency of the surface layer is more excellent.
A-O-Z ^1- (R ^f O) _m- Z ³ (1-1)
In formula (1-1), the definitions of A, Z ¹ , R ^f and m are the same as the definitions of the respective groups 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 (2-1)
_{^{-R f7 -Q 71 - [CH 2}} C (R 71) (- Q 72 -SiR n L 3-n)] y -R 72 (2-2)

In formulas (2-1) and (2-2), the definitions of R, L and n are the same as the definitions of each group in formula (1).

R ^f7 is a perfluoroalkylene group.
The carbon number of the perfluoroalkylene group is preferably 1 to 30, and particularly preferably 1 to 6.
The perfluoroalkylene group may be linear or branched.
As R ^f7 , —CF ₂ CF ₂ CF ₂ CF ₂ — or —CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ — is preferable from the viewpoint of easy production of the compound.

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

X is a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom or a di- to octa-valent organopolysiloxane residue.
The above-mentioned 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 carbon number of the alkylene group represented by X is preferably 1 to 20, and particularly preferably 1 to 10.
Examples of the divalent to octavalent organopolysiloxane residue include divalent organopolysiloxane residues and (w + 1) -valent organopolysiloxane residues described later.

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

R ⁷ is a hydroxyl group or an alkyl group.
The carbon number 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 divalent to octavalent organopolysiloxane residue, h is an integer of 1 to 7, i is an integer of 0 to 6, and h + i = 1 to 7.
When (-Q ^b -SiR _n L _3-n ) is two or more, two or more (-Q ^b -SiR _n L _3-n ) may be different. When two or more R ^{7 s} are present, two or more (-R ^{7 s} ) may be different.

Q ⁷¹ is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon atoms and carbon atoms of an alkylene group having 2 or more carbon atoms, and a single bond is preferable from the viewpoint of easily producing a compound.
The carbon number of the alkylene group is preferably 1 to 10, and particularly preferably 2 to 6.
The carbon number of the group having an etheric oxygen atom between carbon atoms and 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 easily producing a compound.
As an alkyl group, a methyl group is preferable.

Q ⁷² is a single bond or an alkylene group. The carbon number of the alkylene group is preferably 1 to 10, and particularly preferably 1 to 6. In terms of easy production of the compound, Q ⁷² is preferably a single bond or -CH _2- .

R ⁷² is a hydrogen atom or a halogen atom, and a hydrogen atom is preferable from the viewpoint of easily producing a compound.

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

As the group (2-1), groups (2-1-1) to (2-1-6) are preferable.
-R ^f7- (X ¹ ) _p -Q ¹ -SiR _n L _3-n (2-1-1)
-R ^f7- (X ² ) _r -Q ²¹ -N [-Q ²² -SiR _n L _3-n ] ₂ (2-1-2)
-R ^f7 -Q ³¹ -G (R ³ ) [-Q ³² -SiR _n L _3-n ] ₂ (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 (2-1-4 )
-R ^f7 -Q ⁵¹ -Si [-Q ⁵² -SiR _n L _3-n ] ₃ (2-1-5)
-R ^f7- [C (O) N (R ^d )] _v -Q ⁶¹ -Z ³ [-Q ⁶² -SiR _n L _3-n ] _w (2-1-6)
In the formulas (2-1-1) to (2-1-6), the definitions of R ^f7 , R, L and n are as described above.

X ¹ is —O— or —C (O) N (R ^d ) — (wherein N is bonded 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 —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group, it is preferable to have these groups between carbon atoms and carbon atoms.

The carbon number of the alkylene group represented by Q ¹ is preferably 1 to 10, and particularly preferably 2 to 6.

As 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. When (X ¹ ) _p is —O—, —CH ₂ CH ₂ CH ₂ — or —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — is preferable. When (X ¹ ) _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 ). A compound is easy to manufacture as Q ¹ is these groups.

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 etheric oxygen atom, —C (O) —, —C (O) O— or —OC (between carbon atom and carbon atom of alkylene group having 2 or more carbon atoms) O) a group having-or -NH-.
The carbon number of the alkylene group represented by Q ²¹ is preferably 1 to 10, and particularly preferably 2 to 6.
An etheric oxygen atom, -C (O)-, -C (O) O-, -OC (O)-or -NH, between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ²¹ 2-10 are preferable and, as for carbon number of group which has-, 2-6 are especially preferable.

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 is bonded to N)).

r is 0 or 1 (however, it is 0 when Q ²¹ is a single bond). In terms of easy production of the compound, 0 is preferable.

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

As Q ²² , —CH ₂ CH ₂ CH ₂ — and —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — are preferable from the viewpoint of easy production of the compound (however, the right side is bonded to Si).

The two [-Q ²² -SiR _n L _3-n ] may be 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 etheric oxygen atom between carbon atoms and 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 the compound.
The alkylene group represented by Q ³¹ is preferably 1-10, 2-6 being particularly preferred.
The carbon number of the group having an etheric oxygen atom between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ³¹ is preferably 2 to 10, and particularly preferably 2 to 6.

G is a carbon atom or a silicon atom.
R ⁶ is a hydroxyl group or an alkyl group. The carbon number of the alkyl group represented by R ³ is preferably 1 to 4.
As G (R ³ ), C (OH) or Si (R ^3a ) (wherein R ^3a is an alkyl group) from the viewpoint of easy production of the compound, wherein the alkyl group preferably has 1 to 10 carbon atoms, and methyl Groups are particularly preferred).

Q ³² is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms and carbon atoms of an alkylene group having 2 or more carbon atoms.
The carbon number of the alkylene group represented by Q ³² is preferably 1 to 10, and particularly preferably 2 to 6.
The carbon number of the group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms and a carbon atom of an alkylene group having 2 or more carbon atoms represented by Q ³² is preferably 2 to 10, 6 is particularly preferred.
From the viewpoint of easy production of the compound, Q ³² is preferably —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, or —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —.
The two [-Q ³² -SiR _n L _3-n ] may be different.

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

The definition of R ^d in the formula (2-1-4) is as described above.
s is 0 or 1.
Q ⁴¹ is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon atoms and carbon atoms of an alkylene group having 2 or more carbon atoms.
The alkylene group represented by Q ⁴¹ is preferably 1-10, 2-6 being particularly preferred.
The carbon number of the group having an etheric oxygen atom between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁴¹ is preferably 2 to 10, and particularly preferably 2 to 6.
t is 0 or 1 (however, it is 0 when Q ⁴¹ is a single bond).
-Q ⁴¹ - _{(O) t} - as is from the viewpoint of easily producing the compound, if s is 0, a single _{bond, -CH 2 O -, - CH} 2 OCH 2 -, - CH 2 OCH 2 CH 2 O-, -CH ₂ OCH ₂ CH ₂ OCH _2- , -CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ -is preferable (provided that the left side is bonded to R ^f7 ), and when s is 1, single _{bond, -CH 2 -, - CH 2} CH 2 - is preferred.

Q ⁴² is an alkylene group, and the alkylene group is —O—, —C (O) N (R ^d ) — [R ^{d is} as defined above. And may have a silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group.
When the alkylene group has an —O— or silphenylene skeleton group, it preferably has —O— or a silphenylene skeleton group between carbon atoms and carbon atoms. Further, the alkylene group is -C (O) N (R d ) -, when having a dialkyl silylene or a divalent organopolysiloxane residue, carbon atoms - a terminal of a side that binds between carbon atoms or (O) _u1 Preferably have these groups.
The alkylene group represented by Q ⁴² is preferably 1-10, 2-6 being 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 different.

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

Q ⁵¹ is an alkylene group or a group having an etheric oxygen atom between carbon atoms and carbon atoms of an alkylene group having 2 or more carbon atoms.
The alkylene group represented by Q ⁵¹ is preferably 1-10, 2-6 being particularly preferred.
The carbon number of the group having an etheric oxygen atom between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁵¹ is preferably 2 to 10, and particularly preferably 2 to 6.
As Q ⁵¹ , from the viewpoint of easy production of 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 (but the right side is bonded to Si).

Q ⁵² is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms and carbon atoms of an alkylene group having 2 or more carbon atoms.
The alkylene group represented by Q ⁵² is preferably 1-10, 2-6 being particularly preferred.
The carbon number of the group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms and a carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁵² is preferably 2 to 10, 6 is particularly preferred.
Q ⁵² is preferably —CH ₂ CH ₂ CH ₂ — or —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — from the viewpoint of easy production of the compound (however, the right side is bonded to SiR _n L _3-n ).

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

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

The definition of R ^d in formula (2-1-6) is as described above.
v is 0 or 1.

Q ⁶¹ is an alkylene group or a group having an etheric oxygen atom between carbon atoms and carbon atoms of an alkylene group having 2 or more carbon atoms.
The alkylene group represented by Q ⁶¹ is preferably 1-10, 2-6 being particularly preferred.
The carbon number of the group having an etheric oxygen atom between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁶¹ is preferably 2 to 10, and particularly preferably 2 to 6.
As Q ⁶¹ , in view of easy production of 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 (but the right side is bound to Z ³ ).

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

Q ⁶² is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms and carbon atoms of an alkylene group having 2 or more carbon atoms.
The alkylene group represented by Q ⁶² is preferably 1-10, 2-6 being particularly preferred.
The carbon number of the group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms and a carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ⁶² is preferably 2 to 10, 6 is particularly preferred.
As Q ⁶² , —CH ₂ CH ₂ — and —CH ₂ CH ₂ CH ₂ — are preferable from the viewpoint of easy production of the compound.

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

Specific examples of the compound (1) include those described in the following documents.
Perfluoropolyether-modified aminosilane described in JP-A-11-029 585, Silicon-containing organic fluorine-containing polymer described in JP-B-2874715, Organosilicon compound described in JP-A-2000-144097, JP-A-2000- Perfluoropolyether-modified aminosilane described in JP-A-327772, fluorinated siloxane described in JP-A-2002-506887, organosilicon compound described in JP-A-2008-534696, fluorine disclosed in JP-B-4138936 -Modified hydrogen-containing polymer, US Patent Application Publication No. 2010/0129672, International Publication No. 2014/126064, compounds described in Japanese Patent Application Laid-Open No. 2014-070163, International Publication No. 2011060047, International Publication No. 2011/05 Organosilicon compounds described in No. 430, fluorine-containing organosilane compounds described in WO 2012/064649, fluorooxyalkylene group-containing polymers described in JP 2012-72272 A, WO 2013/042732, WO 2013/121984, WO 2013/121985, WO 2013/121986, WO 2014/163004, JP 2014-080473, WO 2015/087902, WO The fluorine-containing ether compounds described in No. 2017/038830, International Publication No. 2017/038832, International Publication No. 2017/187775, JP-A-2014-218639, International Publication No. 2017/022437, International Publication No. 201 Perfluoro (poly) ether-containing silane compounds described in JP-A-079743, WO2018 / 143433, JP-A-2015-199906, JP-A-2016-204656, JP-A-2016-210854, JP-A The fluoropolyether group-containing polymer modified silane described in 2016-222859, Japanese Patent Application No. 2017-104731, Japanese Patent Application No. 2017-159696, Japanese Patent Application No. 2017-159697, Japanese Patent Application No. 2017-159698, Japanese Patent Application No. 2017-167973, Japanese Patent Application No. 2017 Fluorine-containing ether compounds described in Japanese Patent Application No. 2017-251611.

A commercial item can also be used for a fluorine-containing ether compound. For example, KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., Optool (registered trademark) DSX manufactured by Daikin Industries, Ltd., Optool (registered trademark) AES, Optool (registered trademark) UF 503, Optool (registered trademark) UD 509, Afluid (registered trademark) S550 manufactured by AGC, Inc. can be mentioned.

The article with a functional layer of the present invention is an article with a functional layer with excellent durability in which the temporal deterioration of the performance of the surface layer is suppressed by having the above-mentioned intermediate layer. For example, when the surface layer has water and oil repellency, a water contact angle can be mentioned as an index for achieving water repellency. The water contact angle of the air-side surface of the surface layer is preferably 100 degrees or more, more preferably 105 degrees or more, still more 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. The water contact angle of the surface layer is preferably as high as possible, so the upper limit is not particularly limited. The water contact angle is measured using a contact angle measurement 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.) in accordance with JIS L 0849: 2013 (ISO 105-X 12: 2001) for the surface on the air side of the surface layer It is preferable to be able to maintain the water contact angle at 100 degrees or more after reciprocating steel wool Bonstar (number: # 0000, dimensions: 5 mm x 10 mm x 10 mm) at a load of 9.8 N and speed: 80 rpm 3,000 times. More preferably, it can be maintained at 105 degrees or more.

The article with a functional layer of the present invention has, for example, the value obtained by subtracting the water contact angle of the surface layer after 3,000 cycles of reciprocation from the initial water contact angle (contact angle reduction amount) for the surface on the air side of the surface layer. It is preferably 25 degrees or less, more preferably 15 degrees or less, and particularly preferably 10 degrees or less. The lower the contact angle reduction amount, the more preferable, and the lower limit value is not particularly limited.

The article with a functional layer of the present invention is assumed to be excellent in durability because the hardness measured on the air-side surface of the surface layer, for example, the Martens hardness, is high. In the article with a functional layer of the present invention, an indentation test apparatus (Fisher's Picodenta HM500) is used for the surface on the air side of the surface layer, 0.03 mN in indentation load, 5 seconds in holding time, loading speed and unloading 8,500 MPa or more is preferable and, as for the Martens hardness measured as speed | rate 0.05 mN / 5 second, 10,000 MPa or more is more preferable.

[Method for producing article with functional layer]
Examples of the method for producing an article with a functional layer of the present invention include a method of forming the above-mentioned intermediate layer and forming a surface layer on the surface of the intermediate layer using the above-mentioned reactive group-containing organic compound.

(Formation of middle layer)
The formation method of the intermediate layer is not particularly limited, and dry coating or wet coating may be mentioned, and dry coating is preferable in that the Al content in the surface region of the intermediate layer can be easily adjusted and the hardness of the layer can be increased.

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

When forming an intermediate | middle layer by dry coating, a vacuum evaporation method or sputtering method is preferable, and the sputtering method is especially preferable from the point which can form the functional layer which is favorable in the reactivity with a surface layer, and excellent in durability.

Specific methods for forming the intermediate layer by vacuum deposition include a method of co-evaporating silicon oxide and aluminum oxide, a method of vapor-depositing a mixture of silicon oxide and aluminum oxide, etc. It can be mentioned.

The temperature for vacuum deposition is preferably 20 to 300 ° C., and particularly preferably 30 to 200 ° C. The pressure for vacuum deposition is preferably 1 × 10 ⁻¹ Pa or less, and particularly preferably 1 × 10 ⁻² Pa or less.

As a specific method for forming the intermediate layer by sputtering, there may be mentioned a method of selecting a sputtering target and an atmosphere 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 percent of Al is 55 to 98 atomic percent with respect to the total amount of silicon atoms (Si) and aluminum atoms (Al) is used. A film can be formed by performing reactive sputtering in a high sputtering gas. As a sputtering gas in this case, a mixed gas of Ar and oxygen is preferably used.

In addition, using two types of targets, a single Si target and a single Al target, the input power is changed for each target to adjust the content ratio of Si and Al in the obtained intermediate layer. May be Also in this case, the intermediate layer can be formed by performing reactive sputtering in a sputtering gas in which the oxidizing gas concentration is sufficiently high.

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

Also in this method, a precursor layer may be formed using two types of targets consisting of Si single substance and Al single substance, and then an oxidation reaction may be performed.

For wet coating, sol gel method, spin coat method, wipe coat method, spray coat method, squeegee coat method, dip coat method, die coat method, ink jet method, flow coat method, roll coat method, cast method, Langmuir Bloget method And gravure coating methods.

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

(Formation of surface layer)
After forming the intermediate layer, the surface is formed by wet coating or dry coating a reactive group-containing organic compound on the surface.

The dry coating includes the same method as in the case of the above-mentioned intermediate layer, and in the reactive group-containing organic compound, when the group is a hydrolyzable silyl group, the decomposition of the compound can be suppressed, and an apparatus Vacuum evaporation is particularly preferred from the viewpoint of simplicity. At the time of vacuum deposition, it is possible to use a porous material such as iron or steel containing a reactive group-containing organic compound or a composition containing the same, or a pellet-like substance impregnated with a solution or dispersion obtained by adding a solvent thereto. Good.

The temperature for vacuum deposition is preferably 20 to 300 ° C., and particularly preferably 30 to 200 ° C. The pressure for vacuum deposition is preferably 1 × 10 ⁻¹ Pa or less, and particularly preferably 1 × 10 ⁻² Pa or less.

In the dry coating, the reactive group-containing organic compound may be used alone, or may be used as a mixture of two or more of the reactive group-containing organic compounds, and the reactive group-containing organic compound and the other components (however, And the like, or may be used as a solution or a dispersion obtained by adding a solvent thereto.

As wet coating, the method similar to the case of the intermediate | middle layer mentioned above is mentioned. In wet coating, a coating solution for forming a surface layer is preferably used. The coating solution for forming a surface layer is a solution or dispersion containing a reactive group-containing organic compound and a solvent.

A solvent is suitably selected according to the kind of reactive group containing organic compound. 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, may be a non-fluorinated organic solvent, or may be a mixture of both solvents. The fluorinated organic solvent may, for example, be a fluorinated alkane, a fluorinated aromatic compound, a fluoroalkyl ether, a fluorinated alkylamine or a fluoroalcohol.

As the non-fluorinated organic solvent, a compound composed of only hydrogen atom and carbon atom and a compound composed of only hydrogen atom, carbon atom and oxygen atom are preferable, and a hydrocarbon based organic solvent, an alcohol based organic solvent, a ketone based organic solvent, Ether-based organic solvents and ester-based organic solvents can be mentioned.

The coating solution for forming the surface layer was formed in the process of producing the compound having the other components and impurities (hydrolyzable silyl group), as long as the effects of the present invention are not impaired in addition to the reactive group-containing organic compound and the solvent. By-products etc. may be included. As another component, for example, in the case of a reactive group-containing organic compound, when the group is a hydrolyzable silyl group, an acid catalyst or a basic catalyst which promotes the hydrolysis and condensation reaction of the hydrolyzable silyl group Are known additives.

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

<Post-processing>
In order to improve the abrasion resistance of the surface layer, an operation for accelerating the reaction between the reactive group-containing organic compound and the intermediate layer may be performed, if necessary. Examples of the operation include heating, humidification, light irradiation and the like. For example, in the case of a reactive group-containing organic compound, when the group is a hydrolyzable silyl group, the intermediate layer-formed substrate on which the surface layer is formed is heated in the atmosphere having water to be hydrolyzable silyl. Hydrolysis reaction of silanol group to silanol group, formation of siloxane bond by condensation reaction of silanol group, condensation reaction of silanol group on the surface of intermediate layer, Al-OH group etc with silanol group of compound having hydrolyzable silyl group Etc. can be promoted.

After the surface treatment, compounds in the surface layer which are not chemically bonded to other compounds or the intermediate layer may be removed as necessary. As a specific method, for example, a method of pouring a solvent over the surface layer, a method of wiping with a cloth impregnated with a solvent, and the like can be mentioned.

[Use]
The article with a functional layer of the present invention is preferably used for articles for transport equipment, articles for precision instruments, articles for optical instruments, articles for construction, or articles for electronic devices. In addition, the article with a functional layer of the present invention may be used for articles other than the various devices described above.

Specific examples of the article for transport equipment include exterior members, interior members, glass (for example, front glass, side glass and rear glass), mirrors, tire wheels in trains, automobiles, ships, aircraft and the like. A specific example of the article for precision instruments is a window material in a photographing instrument. Specific examples of the article for an optical device include lenses such as glasses and a camera. A window, a floor material, a wall material, and a door material are mentioned as a specific example of the article for construction. Specific examples of the article for an electronic device include a glass for a display in a communication terminal or an image display device, a protective film for a display, an antireflective film, and a fingerprint sensor.

According to the present invention, an intermediate layer containing silicon oxide and aluminum oxide is formed on the surface of a substrate, and a surface layer is formed by wet-coating or dry-coating a reactive group-containing organic compound on the intermediate layer. A method of obtaining an article with a functional layer comprising a functional layer including the intermediate layer and the surface layer directly laminated on the intermediate layer, wherein the depth obtained by 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 is 5 atomic% or less for the first time at each depth point in the longitudinal profile In the region of 1.0 to 3.0 nm in the vertical direction, the average value of the ratio of aluminum atoms to the total number of silicon atoms and aluminum atoms is Is 55 to 98 atomic%, the production method of the functional layer with article is provided.
The description of each component in the above-described manufacturing method is the same as that described above, and thus is 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 6 are Examples, and Examples 7 to 10 are Comparative Examples.

In each example, the following materials were used to produce an article with a functional layer having water and oil repellency as the performance, and the following physical property measurement and evaluation were performed.
[material]
Base material; sapphire substrate (100 mmφ, thickness 0.8 mm, manufactured by Shinko Co., Ltd.)
Reactive group-containing organic compound; a fluorine-containing ether compound (number average molecular weight: 4,920) represented by the following chemical formula, synthesized by the synthesis method of compound (ii-2) in WO 2014/126064 (hereinafter, “containing It is described as "fluorinated 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 properties and evaluation]
(C content, Al content and thickness of intermediate layer)
The C content, the Al content, and the thickness of the intermediate layer were calculated by the following apparatus, measurement conditions, and methods. In addition, each measurement was performed once.

<Device>
X-ray photoelectron spectrometer; Quantera-SXM manufactured by ULVAC-PHI
<Measurement conditions>
X-ray source; monochromatized AlK α ray with a beam diameter of about 100 μm, photoelectron detection angle: 45 degrees, path energy; 224 eV
Step energy: 0.4 eV / step
Sputtering ion; Ar ion sputtering gun raster size of 1 kV acceleration voltage; 3 × 3 mm ²
Spacing interval: 1 minute Sputter gun SiO ₂ equivalent sputtering rate on silicon wafer; 0.78 nm / min

<Method>
First, the sputter rate of the SiO ₂ film becomes 1.00 nm / min or less using the SiO ₂ film (standard sample; thermal oxide film manufactured by KS World Inc.) having a known film thickness on a silicon wafer. Thus, the raster size of the sputter gun was adjusted to 3 × 3 mm ² . The sputter rate of the SiO ₂ film with a raster size of 3 × 3 mm ² was 0.78 nm / min.

Then, under the above-described sputtering conditions, a depth direction profile of integrated intensity of C1s, O1s, Al2p, Si2p peaks was obtained from the air side of the functional layer. At this time, the sputtering interval was set to one minute. From the integrated intensity of each peak, the C content and the Al content were calculated using an 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. Further, the depth from the outermost surface on the air side of the functional layer was determined as a SiO ₂ converted value from the sputtering rate obtained in the analysis of the standard sample.
Furthermore, a depth direction profile was created with the ΔSi / O atomic concentration ratio as the vertical axis, and the end point E was determined from the extreme point in the profile. Specifically, in the region deeper than the starting point S viewed from the air side of the functional layer, the maximum in the depth direction profile of the ΔSi / O atomic concentration ratio appeared near the depth region where the Si 2 p peak is not detected The point is taken as the end point E. The depth from the start point S to the end point E was determined, and the thickness of the intermediate layer was calculated.

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

(Martens hardness)
With respect to the surface of the surface layer, Martens hardness (indentation test device (Fisher's, Picodenta HM500), indentation load: 0.03 mN, holding time 5 seconds, loading speed and unloading speed 0.05 mN / 5 seconds, Unit; MPa) was measured. The measurement was performed at three different places on the surface of the surface layer, and the average value was calculated.

(Steel wool wear test)
For the surface layer, using a reciprocating traverse tester (manufactured by Daiei Seiki Co., Ltd.) in accordance with JIS L 0849: 2013 (ISO 105-X12: 2001), a steel wool Bonstar (number: # 0000, size: 5 mm x 10 mm x 10 mm) was reciprocated at a speed of 80 rpm and a load of 9.8 N. After 3,000 cycles, the water contact angle of the surface layer was measured and evaluated according to the following criteria.

A: Water contact angle of surface layer after 3,000 cycles of reciprocation is 105 degrees or more B: Water contact angle of surface layer after 3,000 cycles of reciprocation is 100 degrees or more and less than 105 degrees C: after 3,000 cycles of reciprocation Water contact angle of surface layer is less than 100 degrees

Further, the value obtained by subtracting the water contact angle of the surface layer after 3,000 cycles of reciprocation from the initial water contact angle was taken as the contact angle reduction amount. As the water contact angle after abrasion is larger, and as the reduction of the water contact angle due to abrasion (contact angle reduction amount) is smaller, the deterioration of performance due to abrasion is smaller, and the durability is excellent.

[Examples 1-8]
(Cleaning of the substrate (impurity removal))
The sapphire substrate was washed by immersion in an alkaline aqueous solution (Sica clean LX-IV; product name, manufactured by Kanto Kagaku, concentration 10% by mass), and then washed with ion-exchanged water.

(Formation of middle layer)
A post-oxidation method (Japanese Patent Laid-Open No. 2007-248562) is performed on a main surface of the washed sapphire substrate using a load lock sputtering apparatus (RAS-1100 BII, manufactured by Syncron Co., Ltd.) after sputtering of metal. A method of conducting an oxidation reaction was used to form an intermediate layer which was a mixed film of aluminum oxide and silicon oxide, to obtain a sapphire substrate with an intermediate layer. The sputtering apparatus is provided with two film formation chambers and one reaction chamber provided with an RF plasma source. A polycrystalline silicon target was disposed in the film forming chamber 1, and a pure aluminum target was disposed in the film forming chamber 2. The sapphire substrate was fixed to the film formation holder, and evacuation of the load lock chamber was started. After the substrate holder was introduced into the film formation chamber through the load lock chamber, film formation was started when the film formation chamber became 2.0 × 10 ⁻⁴ Pa or less.

In the film formation, sputtering of Si, sputtering of Al, and oxidation reaction were sequentially performed by rotating the film formation holder at 60 prm and conveying the sapphire substrate in the order of the film formation chamber 1, the film formation chamber 2 and the reaction chamber. . In each of the examples, the process gas shown in Table 1 was introduced at a flow rate shown in Table 1 into the film forming chamber 1, the film forming chamber 2 and the reaction chamber. Further, Table 1 shows the amounts of electric power supplied 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. Furthermore, Table 1 shows the substrate temperature and the deposition rate.

In Table 1, 5N and 4N in parentheses after the target indicate the purity. Specifically, 5N is 99.99999% and 4N is 99.9999%.

(Deposition of surface layer)
As a vapor deposition source, 0.5 g of a fluorine-containing ether compound F was placed in a molybdenum boat in a vacuum vapor deposition apparatus (VTR-350M, manufactured by ULVAC KIKO Inc.). The sapphire substrate with the intermediate layer obtained above was placed in a vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was evacuated to a pressure of 5 × 10 ⁻³ Pa or less. The boat was heated to 300 ° C., and the fluorine-containing ether compound F was vacuum deposited on the intermediate layer to form a deposited film. The sapphire substrate with the intermediate layer on which the vapor deposition 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 9]
Silicon oxide (SiO ₂ (C), manufactured by Canon Optron Co., Ltd.) was disposed as a deposition source on a molybdenum boat in a vacuum evaporation apparatus (VTR-350M, manufactured by ULVAC KIKO Inc.). A sapphire substrate washed in the same manner as in Example 1 was placed in a vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was evacuated to a pressure of 5 × 10 ⁻³ Pa or less. The boat was heated to 1,000 ° C., and silicon oxide was vacuum deposited to form a deposited film.

Furthermore, 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 10]
A surface layer was formed in the same manner as in Example 1 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.

The Al content [atomic%] in the surface layer region of the intermediate layer was determined by the above method for the article with a functional layer obtained in each of the above examples. Moreover, about the article with a functional layer obtained by each said example, the measurement by measurement of initial water contact angle, the measurement of Martens hardness, and the steel wool abrasion test was performed by the said method. The results are shown in Table 1.

Moreover, as for the origin S in the article with a functional layer obtained in each said example, all were a point of 0.8 nm in the depth direction from the outermost surface of the article with a functional layer. That is, the thickness of the surface layer obtained by the above-mentioned X-ray photoelectron spectroscopy was 0.8 nm as a SiO ₂ conversion value. Further, 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 conversion value.

As apparent from Table 1, regarding the articles with functional layers obtained in Examples 1 to 6 which are Examples of the present invention, the initial contact angle is at a high level, and the water contact angle after the steel wool abrasion test is also I can maintain a high level.

The article with a functional layer of the present invention is an article with a functional layer having a functional layer consisting of an intermediate layer and a surface layer on a base material, and the deterioration with the passage of time of the performance of the surface layer is suppressed. Excellent. The article with a functional layer of the present invention having such properties is preferably used for articles for transport equipment, articles for precision instruments, articles for optical instruments, articles for construction, or articles for electronic devices. In addition, the article with a functional layer of the present invention may be used for articles other than the various devices described above.
The entire contents of the specification, claims, abstract and drawings of Japanese Patent Application No. 2017-245220 filed on Dec. 21, 2017 are incorporated herein by reference and incorporated as disclosure of the specification of the present invention. It is a thing.

10 ... an article with a functional layer, 1 ... a base material, 2 ... an intermediate layer, 3 ... a surface layer, 4 ... a functional layer

Claims (10)

An article with a functional layer, comprising: a substrate; and a functional layer laminated on the substrate,
A surface layer formed of the interlayer comprising the silicon oxide and the aluminum oxide, and the organic compound having a group capable of reacting with the silicon oxide and the aluminum oxide, which is directly laminated on the interlayer; Is composed of
The ratio of carbon atoms to the total number of carbon atoms, oxygen atoms, aluminum atoms, and silicon atoms at each depth point in the depth direction profile obtained by X-ray photoelectron spectroscopy using ion sputtering in the functional layer is The average value of the ratio of aluminum atoms to the total number of silicon atoms and aluminum atoms in the region from 1.0 to 3.0 nm in the depth direction starting from the depth point where the first reduction to 5 atomic% or less Is 55 to 98 atomic%, an article with a functional layer. The article according to claim 1, wherein the organic compound is a fluorine-containing compound. The article according to claim 2, wherein the fluorine-containing compound is a compound having a poly (oxyperfluoroalkylene) chain. The article according to any one of claims 1 to 3, wherein the organic compound is an organic compound having one or more groups selected from silanol groups and hydrolyzable silyl groups. The article according to any one of claims 1 to 4, wherein the thickness of the intermediate layer calculated from the depth direction profile obtained by the X-ray photoelectron spectroscopy is 3 to 200 nm. An article according to any of the preceding claims, wherein the substrate comprises sapphire. Form an intermediate layer comprising silicon oxide and aluminum oxide on the surface of the substrate,
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 of obtaining an article with a functional layer, comprising: the intermediate layer and a functional layer including the surface layer directly laminated on the intermediate layer,
The ratio of carbon atoms to the total number of carbon atoms, oxygen atoms, aluminum atoms, and silicon atoms at each depth point in the depth direction profile obtained by X-ray photoelectron spectroscopy using ion sputtering in the functional layer is The average value of the ratio of aluminum atoms to the total number of silicon atoms and aluminum atoms in the region from 1.0 to 3.0 nm in the depth direction starting from the depth point where the first reduction to 5 atomic% or less Is 55 to 98 atomic%, and the method for producing an article with a functional layer. The manufacturing method according to claim 7, wherein the intermediate layer is formed by wet coating. The manufacturing method according to claim 7, wherein the intermediate layer is formed by dry coating. The manufacturing method according to claim 9, wherein the dry coating is a sputtering method.

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