WO2019124269A1 - Article équipé d'une couche fonctionnelle et procédé de fabrication d'un article équipé d'une couche fonctionnelle - Google Patents

Article équipé d'une couche fonctionnelle et procédé de fabrication d'un article équipé d'une couche fonctionnelle Download PDF

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WO2019124269A1
WO2019124269A1 PCT/JP2018/046167 JP2018046167W WO2019124269A1 WO 2019124269 A1 WO2019124269 A1 WO 2019124269A1 JP 2018046167 W JP2018046167 W JP 2018046167W WO 2019124269 A1 WO2019124269 A1 WO 2019124269A1
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group
layer
functional layer
atoms
intermediate layer
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PCT/JP2018/046167
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English (en)
Japanese (ja)
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万江美 岩橋
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Ａｇｃ株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/10—Glass or silica
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/12—Organic material

Definitions

  • the present invention relates to an article with a functional layer and a method for producing an article with a functional layer.
  • a technique of providing a layer having desired performance on the substrate there is known a technique of providing a layer having desired performance on the substrate.
  • 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.
  • 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.
  • This invention is made from the said viewpoint, Comprising: It makes it a subject to provide the articles
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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-.
  • hydrolyzable silyl group means a group capable of forming a silanol group (Si—OH) by a hydrolysis reaction.
  • Si—OH silanol group
  • 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.
  • 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.
  • 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.
  • 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.
  • the ratio of carbon atoms to the total number of carbon atoms, oxygen atoms, aluminum atoms, and silicon atoms is "C content”
  • the ratio of aluminum atoms to the total number of silicon atoms and aluminum atoms is "Al content”.
  • the surface layer is a layer mainly composed of an organic substance
  • 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.
  • 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”).
  • 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”.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the interface between the intermediate layer and the additional layer is an end point E.
  • 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.
  • at least the main surface on which the intermediate layer is formed be made of sapphire.
  • sapphire means ⁇ -Al 2 O 3 .
  • ⁇ -Al 2 O 3 crystals containing minor components (eg, SiO 2 ) other than ⁇ -Al 2 O 3 and ⁇ -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.
  • the surface of the substrate may be subjected to an activation treatment (for example, a dry activation treatment, a wet activation treatment).
  • an activation treatment for example, a dry activation treatment, a wet activation treatment.
  • 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.
  • active energy rays for example, ultraviolet rays, electron beams, X-rays
  • corona discharge treatment vacuum plasma treatment
  • atmospheric pressure plasma treatment atmospheric pressure plasma treatment
  • flame treatment flame treatment
  • Itro treatment Itro treatment.
  • wet activation treatment include treatment of bringing the surface layer into contact with an acid or alkaline solution.
  • corona discharge treatment is preferable in terms of further improving the adhesion between the substrate and the intermediate layer.
  • 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.
  • 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
  • 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.
  • Start 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.
  • 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 ⁇ ray with a beam diameter of about 100 ⁇ m, photoelectron detection angle: 45 degrees, path energy; 224 eV Sputtering ion; Ar ion with acceleration voltage 1 kV
  • XPS X-ray photoelectron spectroscopy
  • 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.
  • 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.
  • the additional layer provided between the base immediately below the intermediate layer or between the base and the functional layer is an oxide
  • Si / O atomic concentration ratio the ratio of Si atomic concentration to O atomic concentration
  • 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 ⁇ Si / O atomic concentration ratio.
  • a depth profile is created with the ⁇ Si / 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 ⁇ Si / O atomic concentration ratio as the vertical axis.
  • 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 ⁇ Al / Si atomic concentration ratio created in the same procedure as described above.
  • the base immediately below the intermediate layer or between the base 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 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 ⁇ Si / element X atomic concentration ratio created in the same procedure as the vertical axis.
  • 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.
  • the intermediate layer preferably contains substantially no components other than silicon oxide and aluminum oxide.
  • it does not contain actively, but not containing it substantially means that the contamination by an unavoidable impurity is accept
  • 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%.
  • 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
  • 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%.
  • 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.
  • 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.
  • the surface layer in the present invention is formed using a reactive group-containing organic compound.
  • 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.
  • 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).
  • a group capable of forming a hydroxyl group for example, a group in which a hydroxyl group is protected by any protective group.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • fluorine-containing compound examples 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.
  • 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.
  • 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.
  • fluorine-containing compound having a perfluoroalkyl group and a hydrolyzable silyl group examples include compounds represented by the formula (3) described in paragraph [0010] and [0022] of JP-A-2009-139530.
  • 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.
  • the arrangement of the plurality of oxyperfluoroalkylene groups may be block, random or alternating.
  • the carbon number of the oxyperfluoroalkylene group is 2 or more, it is preferably a linear oxyperfluoroalkylene group.
  • 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
  • the fluorine-containing ether compound 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.
  • a compound (1) is preferable at the point which the water-oil repellency of a surface layer is more excellent.
  • 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 .
  • CF 3- 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 3 CF 2 CF 2 CF 2 CF 2- , CF 3 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.
  • L examples 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.
  • a halogen atom a chlorine atom is preferable.
  • an alkoxy group having 1 to 4 carbon atoms and a halogen atom are preferable from the viewpoint of easy industrial production.
  • 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.
  • 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.
  • —Si (OCH 3 ) 3 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.
  • 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.
  • 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 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 O) m19 (CF 2 CF 2 O), ⁇ (CF 2 O) m20 (CF 2 CF 2 CF 2 O) m21 ⁇ , ⁇ (CF 2 CF 2 O)
  • m11 and m12 are each an integer of 1 or more
  • m13 and m14 are each an integer of 0 or 1
  • m11 + m12 + m13 + m14 is an integer of 2 to 200
  • 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 O is not limited.
  • m16 and m17 are each an integer of 2 to 200
  • 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
  • -R f7 -Q 71 [CH 2 C (R 71) (- Q 72 -SiR n L 3-n)] y -R 72 (2-2)
  • 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.
  • 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 .
  • 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.
  • (-Q b -SiR n L 3-n ) is two or more, two or more (-Q b -SiR n L 3-n ) may be different.
  • 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.
  • a hydrogen atom is preferable from the viewpoint of easily producing a compound.
  • 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.
  • 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.
  • groups (2-1-1) to (2-1-6) are preferable.
  • X 1 is —O— or —C (O) N (R d ) — (wherein N is bonded to Q 1 ).
  • 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.
  • 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.
  • group (2-1-1) include the following groups.
  • X 2 is —O—, —NH— or —C (O) N (R d ) —.
  • 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.
  • 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.
  • —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.
  • 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.
  • 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.
  • 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 —.
  • the two [-Q 32 -SiR n L 3-n ] may be different.
  • group (2-1-3) include the following groups.
  • 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 - 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • group (2-1-5) include the following groups.
  • 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.
  • 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.
  • 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.
  • 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.
  • a commercial item can also be used for a fluorine-containing ether compound.
  • KY-100 series KY-178, KY-185, KY-195, etc.
  • Optool (registered trademark) DSX manufactured by Daikin Industries, Ltd.
  • Optool (registered trademark) AES manufactured by Daikin Industries, Ltd.
  • Optool (registered trademark) UF 503 manufactured by Daikin Industries, Ltd.
  • Optool (registered trademark) UD 509 Afluid (registered trademark) S550 manufactured by AGC, Inc.
  • 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.
  • 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
  • a reciprocating traverse tester manufactured by Daiei Seiki Co., Ltd.
  • JIS L 0849: 2013 ISO 105-X 12: 2001
  • 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.
  • 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
  • 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.
  • 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.
  • dry coating examples 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.
  • 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.
  • 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.
  • 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.
  • a sputtering gas in this case, a mixed gas of Ar and oxygen is preferably used.
  • the input power is changed for each target to adjust the content ratio of Si and Al in the obtained intermediate layer.
  • the intermediate layer can be formed by performing reactive sputtering in a sputtering gas in which the oxidizing gas concentration is sufficiently high.
  • 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
  • an inert gas such as Ar gas
  • oxygen may be reacted with the precursor layer using, for example, a radio frequency (RF) plasma to form an intermediate layer.
  • RF radio frequency
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • an operation for accelerating the reaction between the reactive group-containing organic compound and the intermediate layer may be performed, if necessary.
  • the operation include heating, humidification, light irradiation and the like.
  • the intermediate layer-formed substrate on which the surface layer is formed is heated in the atmosphere having water to be hydrolyzable silyl.
  • compounds in the surface layer which are not chemically bonded to other compounds or the intermediate layer may be removed as necessary.
  • 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.
  • 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.
  • the article with a functional layer of the present invention may be used for articles other than the various devices described above.
  • 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.
  • 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
  • Examples 1 to 6 are Examples, and Examples 7 to 10 are Comparative Examples.
  • 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.
  • 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.
  • 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.
  • a depth direction profile of integrated intensity of C1s, O1s, Al2p, Si2p peaks was obtained from the air side of the functional layer.
  • the sputtering interval was set to one minute.
  • 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.
  • 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.
  • a depth direction profile was created with the ⁇ Si / 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 ⁇ Si / 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.
  • 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.
  • Step 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
  • 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.
  • 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.
  • Example 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.
  • an alkaline aqueous solution Sica clean LX-IV; product name, manufactured by Kanto Kagaku, concentration 10% by mass
  • 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.
  • 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.
  • 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.
  • 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.
  • Table 1 shows the substrate temperature and the deposition rate.
  • a fluorine-containing ether compound F 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.
  • VTR-350M vacuum vapor deposition apparatus
  • 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.
  • VTR-350M vacuum evaporation apparatus
  • Example 2 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.
  • 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.
  • the initial contact angle is at a high level
  • 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.
  • the article with a functional layer of the present invention may be used for articles other than the various devices described above.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
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Abstract

La présente invention concerne un article équipé d'une couche fonctionnelle, dans lequel la diminution de performance de la couche fonctionnelle au fil du temps est réduite au minimum, ce qui permet d'obtenir une excellente durabilité. L'invention concerne un article équipé d'une couche fonctionnelle présentant un substrat et une couche fonctionnelle stratifiée sur le substrat, la couche fonctionnelle comprenant une couche intermédiaire contenant de l'oxyde de silicium et de l'oxyde d'aluminium, et une couche de surface, qui est directement stratifiée sur la couche intermédiaire et qui est formée à l'aide d'un composé organique ayant un groupe capable de réagir avec de l'oxyde de silicium et de l'oxyde d'aluminium ; et lorsque le point de profondeur, parmi les points de profondeur d'un profil de direction de profondeur acquis par spectroscopie photoélectronique à rayons X dans la couche fonctionnelle, au niveau duquel la proportion d'atomes de C par rapport au nombre total d'atomes de C, O, Al et de Si atteint d'abord 5 % d'atome, est considéré comme étant l'origine, la valeur moyenne de la proportion d'atomes d'Al par rapport au nombre total d'atomes de Si et d'Al dans une région de 1,0 à 3,0 nm dans la direction de profondeur à partir de l'origine est de 55 à 98 % atomique.
PCT/JP2018/046167 2017-12-21 2018-12-14 Article équipé d'une couche fonctionnelle et procédé de fabrication d'un article équipé d'une couche fonctionnelle WO2019124269A1 (fr)

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JPH02258646A (ja) * 1988-12-15 1990-10-19 Nissan Chem Ind Ltd コーティング用組成物及びその製造法
JP2006276617A (ja) * 2005-03-30 2006-10-12 Sumitomo Chemical Co Ltd 偏光変換素子及びそれを用いた投射型液晶表示装置
JP2014181404A (ja) * 2013-03-15 2014-09-29 Apple Inc サファイア基板のための積層コーティング
JP2014218639A (ja) * 2012-11-05 2014-11-20 ダイキン工業株式会社 パーフルオロ（ポリ）エーテル基含有シラン化合物
WO2015182657A1 (fr) * 2014-05-29 2015-12-03 日産化学工業株式会社 Agent de formation d'un revêtement adhésif destiné à un substrat d'oxyde d'aluminium ou d'aluminium
JP2016500030A (ja) * 2012-09-21 2016-01-07 アップル インコーポレイテッド サファイア上での撥油性コーティング
WO2016133038A1 (fr) * 2015-02-20 2016-08-25 東洋紡株式会社 Film barrière transparent
JP2016182751A (ja) * 2015-03-26 2016-10-20 京セラディスプレイ株式会社 表面被覆物品
WO2017022638A1 (fr) * 2015-07-31 2017-02-09 日産化学工業株式会社 Substrat de verre approprié en tant que verre de protection, etc., d'un dispositif d'affichage mobile
WO2017195811A1 (fr) * 2016-05-10 2017-11-16 株式会社神戸製鋼所 Matériau en alliage d'aluminium, matériau en alliage d'aluminium ayant une couche de résine adhésive, procédé de production de matériau en alliage d'aluminium, et procédé de production de matériau en alliage d'aluminium ayant une couche de résine adhésive

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02258646A (ja) * 1988-12-15 1990-10-19 Nissan Chem Ind Ltd コーティング用組成物及びその製造法
JP2006276617A (ja) * 2005-03-30 2006-10-12 Sumitomo Chemical Co Ltd 偏光変換素子及びそれを用いた投射型液晶表示装置
JP2016500030A (ja) * 2012-09-21 2016-01-07 アップル インコーポレイテッド サファイア上での撥油性コーティング
JP2014218639A (ja) * 2012-11-05 2014-11-20 ダイキン工業株式会社 パーフルオロ（ポリ）エーテル基含有シラン化合物
JP2014181404A (ja) * 2013-03-15 2014-09-29 Apple Inc サファイア基板のための積層コーティング
WO2015182657A1 (fr) * 2014-05-29 2015-12-03 日産化学工業株式会社 Agent de formation d'un revêtement adhésif destiné à un substrat d'oxyde d'aluminium ou d'aluminium
WO2016133038A1 (fr) * 2015-02-20 2016-08-25 東洋紡株式会社 Film barrière transparent
JP2016182751A (ja) * 2015-03-26 2016-10-20 京セラディスプレイ株式会社 表面被覆物品
WO2017022638A1 (fr) * 2015-07-31 2017-02-09 日産化学工業株式会社 Substrat de verre approprié en tant que verre de protection, etc., d'un dispositif d'affichage mobile
WO2017195811A1 (fr) * 2016-05-10 2017-11-16 株式会社神戸製鋼所 Matériau en alliage d'aluminium, matériau en alliage d'aluminium ayant une couche de résine adhésive, procédé de production de matériau en alliage d'aluminium, et procédé de production de matériau en alliage d'aluminium ayant une couche de résine adhésive

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