WO2024029537A1 - Substrat doté d'un film de silice - Google Patents

Substrat doté d'un film de silice Download PDF

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Publication number
WO2024029537A1
WO2024029537A1 PCT/JP2023/028164 JP2023028164W WO2024029537A1 WO 2024029537 A1 WO2024029537 A1 WO 2024029537A1 JP 2023028164 W JP2023028164 W JP 2023028164W WO 2024029537 A1 WO2024029537 A1 WO 2024029537A1
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Prior art keywords
silica film
substrate
silica
content
antioxidant
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PCT/JP2023/028164
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English (en)
Japanese (ja)
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彩夏 安部
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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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic

Definitions

  • the present invention relates to a substrate with a silica film.
  • Patent Document 1 discloses a method in which a coating solution containing methyltriethoxysilane, an aqueous hydrochloric acid solution, and ethanol is applied onto a substrate such as a glass substrate or a stainless steel plate, and dried to form a water- and oil-repellent film on the substrate. is disclosed.
  • the present invention was made in view of the above problems, and an object of the present invention is to provide a substrate with a silica film that has excellent initial oil repellency and improved oil repellency after heating to 300°C.
  • the silica film of the silica film-coated substrate contains a hydrolyzed condensate of a hydrolyzable compound including a compound represented by a predetermined formula, and an antioxidant. found that the desired effect can be obtained when the ratio of the carbon atom content to the silicon atom content in the silica film is 0.90 or more and the thickness of the silica film is 15 nm or more, and the present invention reached.
  • [1] Includes a substrate and a silica film disposed on the substrate,
  • the silica membrane contains a hydrolyzed condensate of a hydrolyzable compound including a compound represented by formula (1), and an antioxidant,
  • the content of the antioxidant is 25% by mass or less based on the total mass of the silica film,
  • the ratio of the content of carbon atoms to the content of silicon atoms in the silica film is 0.90 or more
  • R 1 is an alkyl group having 1 to 3 carbon atoms
  • R 2 is a methyl group or an ethyl group
  • n is an integer from 1 to 3.
  • [4] The silica film-coated substrate according to any one of [1] to [3], wherein the silica film has a thickness of 120 nm or less.
  • [5] The silica film-coated substrate according to any one of [1] to [4], wherein the antioxidant has a 12% weight loss temperature of 300° C. or higher when measured in air.
  • [6] The silica film-coated substrate according to any one of [1] to [5], wherein the silica film contains two or more types of antioxidants having different reaction mechanisms as the antioxidants.
  • [7] The silica film-coated substrate according to any one of [1] to [6], wherein the silica film contains a phenolic antioxidant and a phosphorus antioxidant as the antioxidant.
  • silica film-coated substrate according to any one of [1] to [7], wherein the content of the antioxidant is 0.05 to 25% by mass based on the total mass of the silica film.
  • the present invention it is possible to provide a substrate with a silica film that has excellent initial oil repellency and improved oil repellency after heating to 300°C.
  • FIG. 1 is a cross-sectional view schematically showing an example of a silica film-coated substrate of the present invention.
  • a numerical range expressed using " ⁇ " means a range that includes the numerical values written before and after " ⁇ " as lower and upper limits.
  • the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise.
  • the upper limit or lower limit described in a certain numerical range may be replaced with the value shown in the Examples.
  • one type of substance corresponding to each component may be used alone, or two or more types may be used in combination.
  • the content of the component refers to the total content of the substances used in combination, unless otherwise specified.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • a silica film-coated substrate of the present invention includes a substrate and a silica film disposed on the substrate. Further, the content of the antioxidant is 25% by mass or less based on the total mass of the silica film. Further, the silica membrane contains a hydrolyzed condensate of a hydrolyzable compound including a compound represented by formula (1) described below, and an antioxidant. Further, the ratio of the content of carbon atoms to the content of silicon atoms in the silica film is 0.90 or more. Further, the thickness of the silica film is 15 nm or more.
  • the silica film-coated substrate of the present invention has excellent initial oil repellency and is also improved in oil repellency after heating to 300° C. (hereinafter also referred to as "oil repellency after heating"). Although the details of this reason have not been clarified, it is assumed that it is generally due to the following reasons.
  • the carbon atoms and silicon atoms contained in the silica membrane of the present invention are mainly based on alkyl groups and siloxane bonds contained in the hydrolyzed condensate of the hydrolyzable compound, respectively.
  • the silica film of the present invention since the ratio of the content of carbon atoms to the content of silicon atoms is 0.90 or more, it is considered that alkyl groups are sufficiently present in the silica film. Therefore, it is presumed that the oil repellency effect due to the alkyl group was well expressed and the initial oil repellency was improved.
  • the siloxane film can suppress thermal decomposition when the silica film is heated. In some cases, the effect of the combination cannot be obtained sufficiently.
  • a silica film containing an antioxidant the effect of the antioxidant suppresses thermal oxidation of the silica film, and as a result, the silica film can exhibit excellent oil repellency even after heating. Guessed. It is also presumed that by using a silica film with a thickness of 15 nm or more, the thickness could be maintained to the extent that excellent oil repellency could be exhibited even after the silica film was heated.
  • FIG. 1 is a cross-sectional view schematically showing an example of a silica film-coated substrate of the present invention.
  • the silica film-coated substrate 1A includes a substrate 10 and a silica film 20 formed on one surface of the substrate 10.
  • the silica film 20 is formed on the entire surface of one side of the substrate 10, but the silica film 20 is not limited to this, and the silica film 20 may be formed only on a part of the surface of the substrate 10.
  • the silica film 20 is formed only on one side of the substrate 10, but the present invention is not limited to this, and the silica film 20 may be formed on both sides of the substrate 10.
  • Each member included in the silica film-coated substrate 1A will be described below.
  • the type of substrate 10 is not particularly limited, a glass substrate and a metal substrate are preferable.
  • materials constituting the glass substrate include soda lime glass, aluminosilicate glass, lithium glass, and borosilicate glass.
  • the glass substrate may be chemically strengthened glass, air-cooled strengthened glass, or crystallized glass.
  • the glass substrate may be a glass plate with a smooth surface formed by a float method or the like, a molded glass plate with an uneven surface, or a glass plate with a curved shape.
  • Specific examples of materials constituting the metal substrate include aluminum, titanium, copper, nickel, stainless steel, brass, magnesium, iron, and alloys thereof. These materials may be used alone or in combination of two or more.
  • the thickness of the substrate 10 is appropriately selected depending on the application and is not particularly limited, but is preferably 0.1 to 50 mm.
  • the thickness of the glass substrate is preferably 1 to 10 mm, more preferably 1 to 5 mm.
  • the thickness of the metal substrate is preferably 0.1 to 50 mm, more preferably 1 to 10 mm.
  • the silica membrane 20 contains a hydrolyzed condensate of a hydrolyzable compound including the compound represented by formula (1), and an antioxidant.
  • the ratio of the carbon atom content to the silicon atom content (carbon atom content/silicon atom content; hereinafter also referred to as "C/Si") in the silica film 20 is 0.90 or more. , 1.00 or more is preferable, 1.20 or more is more preferable, and 1.40 or more is still more preferable, since the initial oil repellency of the silica film-coated substrate 1A is more excellent.
  • C/Si is preferably 1.60 or less, more preferably 1.55 or less, and even more preferably 1.50 or less, from the standpoint that the silica film-coated substrate 1A has better oil repellency after heating.
  • C/Si is determined based on analysis of the surface of the silica film 20 by X-ray photoelectron spectroscopy (XPS) with the angle between the surface of the silica film 20 and the detector being 45 degrees, and specifically, It is calculated as follows.
  • the surface of the silica film 20 is analyzed by X-ray photoelectron spectroscopy (XPS) in which the angle between the surface of the silica film 20 and the detector is 45 degrees, and the peak intensities of Si 2p and C 1s are determined. Based on the obtained peak intensity, the content of silicon atoms (at%) and the content of carbon atoms (at%) are determined, and the concentration of carbon atoms (at%) relative to the content of silicon atoms (at%) is determined. Calculate the ratio of C/Si. Note that detailed measurement conditions for XPS are as described in the Examples section below.
  • the thickness of the silica film 20 is 15 nm or more, preferably 20 nm or more, and 25 nm or more from the viewpoint of better chemical resistance, initial oil repellency, oil repellency after heating, and abrasion resistance of the silica film-coated substrate 1A. More preferred.
  • the thickness of the silica film 20 is preferably 240 nm or less, more preferably 120 nm or less, and even more preferably 100 nm or less, in order to improve the scratch resistance of the silica film-coated substrate 1A.
  • the thickness of the silica film 20 can be measured by the method described in the Examples section using an apparatus based on ellipsometry.
  • silica film 20 examples include protective films for glass substrates and metal substrates (eg, anti-scratch film, antifouling film).
  • hydrolytic condensate of a hydrolyzable compound refers to a compound obtained by hydrolyzing a hydrolyzable group in a hydrolyzable compound and condensing the resulting hydrolyzate.
  • the above-mentioned hydrolyzed condensate is one in which all the hydrolyzable groups are hydrolyzed and all the hydrolysates (compounds obtained by hydrolyzing the hydrolysable groups in the hydrolyzable compound) are condensed. It may be a complete hydrolyzed condensate or a partially hydrolyzed condensate in which some hydrolyzable groups are hydrolyzed and some hydrolysates are condensed.
  • the hydrolyzed condensate may be a complete hydrolyzed condensate, a partially hydrolyzed condensate, or a mixture thereof.
  • a hydrolyzed condensate is a hydrolyzed condensate obtained by condensing hydrolyzable compounds, their hydrolysates, and hydrolyzed condensates of two or more compounds with each other. There may be.
  • the hydrolyzable compound includes a compound represented by formula (1). Si(-R 1 ) n (-OR 2 ) 4-n formula (1)
  • R 1 is an alkyl group having 1 to 3 carbon atoms, specifically a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.
  • R 1 is preferably a methyl group or an ethyl group, and more preferably a methyl group, since the silica film-coated substrate 1A has excellent oil repellency.
  • n is 2 or more, a plurality of R 1 's may be the same or different.
  • R 2 is a methyl group or an ethyl group. That is, the -OR2 group in formula (1) is a methoxy group or an ethoxy group, which is a type of hydrolyzable group.
  • n is 2 or less, a plurality of R 2 's may be the same or different.
  • n is an integer from 1 to 3, and is preferably 1 or 2 from the viewpoint that both the initial oil repellency and the post-heating oil repellency of the silica film-coated substrate 1A can be satisfied at a high level.
  • the compound represented by formula (1) is preferably methyltriethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, or ethyltrimethoxysilane.
  • the compounds represented by formula (1) may be used alone or in combination of two or more.
  • the hydrolyzable compound may contain compounds other than the compound represented by formula (1) (hereinafter also referred to as "other compounds").
  • Other compounds include tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane. Addition of tetraalkoxysilane (tetrafunctional silane) increases bonding points and improves wear resistance.
  • the content of tetraalkoxysilane is preferably 15 to 50% by mass, more preferably 25 to 35% by mass, based on the total mass of the hydrolyzable compound including the compound represented by formula (1).
  • the content of the hydrolyzed condensate is preferably 75 to 99.95% by mass, more preferably 90 to 99.50% by mass, and even more preferably 95 to 99.00% by mass, based on the total mass of the silica membrane 20. .
  • antioxidants include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, and sulfur antioxidants.
  • the antioxidant preferably contains two or more kinds of antioxidants having different reaction mechanisms from each other, from the viewpoint that the silica film-coated substrate 1A has better oil repellency after heating, and includes a phenolic antioxidant and a phosphorus antioxidant. It is more preferable to use both.
  • the expression "the reaction mechanisms are different from each other” means that the reaction mechanisms for suppressing the oxidation of the silica film by the antioxidant are different from each other.
  • an antioxidant whose 12% weight loss temperature when measured in air is 300° C. or higher.
  • the upper limit of the above 12% weight loss temperature is usually 400°C or less.
  • the 12% weight loss temperature of the antioxidant is measured using a thermogravimetric differential thermal analyzer (TG-DTA) at a heating rate of 10° C./min in an air atmosphere.
  • TG-DTA thermogravimetric differential thermal analyzer
  • Specific examples of antioxidants having a 12% weight loss temperature of 300°C or higher when measured in air include 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis.
  • the content of the antioxidant is preferably 0.03% by mass or more, more preferably 0.50% by mass or more, and even more preferably 1.0% by mass or more, based on the total mass of the silica film 20. If the content of the antioxidant is 0.03% by mass or more, the oil repellency of the silica film-coated substrate 1A after heating will be more excellent.
  • the content of the antioxidant is 25% by mass or less, preferably 10% by mass or less, and more preferably 5.0% by mass or less, based on the total mass of the silica film 20. When the content of the silica film is 25% by mass or less, the initial oil repellency and the oil repellency after heating of the silica film-coated substrate 1A are excellent. Furthermore, the appearance characteristics of the silica film are also excellent.
  • the silica film 20 preferably further contains silica particles since the silica film-coated substrate 1A has better wear resistance.
  • Silica particles are particles containing silica (SiO 2 ). Specific examples of the shape of the silica particles include spherical, elliptical, needle-like, plate-like, rod-like, conical, cylindrical, cubic, rectangular, diamond-like, star-like, and irregular shapes. Silica particles may be solid particles, hollow particles, or porous particles. "Solid particle” means a particle that does not have an internal cavity. "Hollow particle” means a particle having a cavity inside. “Porous particle” means a particle having a plurality of pores on its surface. The silica particles may exist independently, each particle may be connected in a chain, or each particle may be aggregated.
  • the average primary particle diameter of the silica particles is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 20 nm or less, from the viewpoint of excellent transparency of the silica film.
  • the average primary particle diameter of the silica particles is preferably 0.1 nm or more, more preferably 0.5 nm or more, and even more preferably 1 nm or more, from the viewpoint of excellent dispersibility in the film.
  • the average primary particle diameter of silica particles is determined by taking an SEM photograph of the particles using a scanning electron microscope (SEM) (for example, an apparatus similar to S-4800 manufactured by Hitachi High Technologies), and determining the long axis of the primary particle in the image. This value is obtained by measuring 100 diameters and taking the arithmetic average. Note that the long axis diameter of the primary particles in the image means the longest line segment when a straight line is drawn from end to end in the primary particles in the image.
  • SEM scanning electron microscope
  • silica particles commercially available products may be used, such as the Snowtex series manufactured by Nissan Chemical Industries, Ltd.
  • the silica particles may be used alone or in combination of two or more.
  • the content of silica particles is preferably 0.05 to 10.00% by mass, more preferably 0.10 to 5.00% by mass, and 0.10 to 1.00% by mass based on the total mass of the silica membrane 20. % is more preferable. If the content of silica particles is 0.05% by mass or more, the wear resistance of the silica film-coated substrate 1A will be better. If the content of silica particles is 10.00% by mass or less, the initial oil repellency of the silica film-coated substrate 1A will be more excellent.
  • the silica film 20 may contain components other than those mentioned above (hereinafter also referred to as "other components"). Specific examples of other components include metal catalysts, acid catalysts (eg, nitric acid), water, alcohols, and other organic solvents.
  • other components include metal catalysts, acid catalysts (eg, nitric acid), water, alcohols, and other organic solvents.
  • the content of the other components is preferably more than 0% by mass and 1.00% by mass or less, and more than 0% by mass and 0.50% by mass, based on the total mass of the silica membrane 20. % or less is more preferable.
  • the silica film-covered substrate 1A may further include an intermediate layer (not shown) between the substrate 10 and the silica film 20.
  • the intermediate layer may be formed on the entire overlapping portion of the substrate 10 and the silica film 20, or may be formed on a part of the overlapping portion of the substrate 10 and the silica film 20.
  • the intermediate layer is preferably a layer that improves the adhesion between the substrate 10 and the silica film 20, and specifically, it is more preferably a layer formed using a silane coupling agent.
  • silane coupling agents include: Tetraethoxysilane, tetramethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyl Epoxysilane such as diethoxysilane; (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane; Vinylsilanes such as vinyltrimethoxysilane, N-2-(N-vinylbenzylaminoethyl)-3
  • Q-configuration or T-configuration silane coupling agents are preferred from the viewpoint of reactivity and adhesion.
  • Commercial products may be used as the silane coupling agent, and specific examples include KBP-90 (product name, manufactured by Shin-Etsu Silicone Co., Ltd., aminosilane) and tetraethoxysilane (Fuji Film Wako Pure Chemical Industries, Ltd.).
  • the intermediate layer may contain a catalyst such as an acid.
  • the thickness of the intermediate layer is preferably 5.00 to 30.00 nm, more preferably 10.00 to 20.00 nm.
  • the thickness of the intermediate layer was determined by acquiring a cross-sectional image of the silica film-coated substrate 1A using a scanning electron microscope (SEM), and measuring the thickness at three different positions corresponding to the thickness of the intermediate layer. Means the arithmetic mean value of the thickness at a location.
  • the contact angle (initial contact angle) of salad oil on the surface of the silica film 20 is preferably 55.0 degrees or more, more preferably 58.0 degrees or more, and still more preferably 60.0 degrees or more. preferable.
  • the upper limit is usually 67.0 degrees or less.
  • the contact angle of salad oil on the surface of the silica film 20 after heating the silica film-coated substrate 1A at 300° C. for 400 hours is preferably 35.0 degrees or more, and 37.0 degrees or more. is more preferable, 40.0 degrees or more is still more preferable, and 50.0 degrees or more is particularly preferable.
  • the upper limit is usually 60.0 degrees or less.
  • the contact angle of salad oil on the surface of the silica film 20 after heating the silica film-coated substrate 1A at 250° C. for 800 hours is preferably 45.0 degrees or more, and preferably 50.0 degrees or more. is more preferable, and even more preferably 55.0 degrees or more.
  • the upper limit is usually 60.0 degrees or less.
  • the contact angle of salad oil on the surface of the silica film 20 after immersing the silica film-coated substrate 1A in a 0.1N aqueous sodium hydroxide solution adjusted to 25° C. for 2 hours is 40.0. It is preferably at least 45.0 degrees, more preferably at least 50.0 degrees.
  • the upper limit is usually 60.0 degrees or less.
  • the contact angle of salad oil on the surface of these silica films 20 is measured by the method described in the Examples section below.
  • the contact angle (initial contact angle) of salad oil on the surface of the silica film 20 is preferably 55.0 degrees or more, more preferably 58.0 degrees or more, and still more preferably 60.0 degrees or more. preferable.
  • the upper limit is usually 67.0 degrees or less.
  • the contact angle of salad oil on the surface of the silica film 20 after heating the silica film-coated substrate 1A at 300° C. for 400 hours is preferably 21.0 degrees or more, and preferably 22.0 degrees or more. is more preferable, 23.0 degrees or more is even more preferable, and 24.0 degrees or more is particularly preferable.
  • the upper limit is usually 40.0 degrees or less.
  • the contact angle of salad oil on the surface of the silica film 20 after heating the silica film-coated substrate 1A at 250° C. for 800 hours is preferably 47.0 degrees or more, and preferably 48.0 degrees or more. is more preferable, and even more preferably 49.0 degrees or more.
  • the upper limit is usually 55.0 degrees or less.
  • the contact angle of salad oil on the surface of these silica films 20 is measured by the method described in the Examples section below.
  • the use of the silica film-coated substrate 1A is not particularly limited, but because of its excellent initial oil repellency and oil repellency during heating, it can be used as a stain-proofing member for use on the inside surface of cooking utensils (e.g. ovens, ranges, grills). It is suitable for antifouling members used on the surfaces of kitchen members (for example, stoves, tiles) and antifouling members used for members of machine tools.
  • Examples of the method for manufacturing the silica film-coated substrate 1A include a method in which a silica film-forming composition is applied onto the substrate 10 and dried if necessary to form the silica film 20 on the substrate 10.
  • composition for forming a silica film includes hydrolyzable compounds and an antioxidant.
  • the hydrolyzable compound is at least one selected from the group consisting of a hydrolyzable compound including the compound represented by formula (1), a hydrolyzate thereof, and a hydrolyzed condensate thereof.
  • a hydrolyzable compound including the compound represented by formula (1) is at least one selected from the group consisting of a hydrolyzable compound including the compound represented by formula (1), a hydrolyzate thereof, and a hydrolyzed condensate thereof.
  • Specific examples and preferred embodiments of the hydrolyzable compound including the compound represented by formula (1) are as described above, so their explanation will be omitted.
  • the composition for forming a silica film contains a compound in which n in formula (1) is 1 (for example, methyltrimethoxysilane) and a compound in which n in formula (1) is 2 (for example, dimethyl It is preferable to include a hydrolyzed condensate with dimethoxysilane) and a compound in which n in formula (1) is 1 (for example, methyltriethoxysilane, ethyltriethoxysilane) as a hydrolyzable compound.
  • a hydrolyzed condensate with dimethoxysilane for example, methyltriethoxysilane, ethyltriethoxysilane
  • hydrolyzate of a hydrolyzable compound refers to a compound obtained by hydrolyzing a hydrolyzable group in a hydrolyzable compound.
  • the above hydrolysates may be those in which all of the hydrolyzable groups have been hydrolyzed (completely hydrolyzed products) or those in which some of the hydrolyzable groups have been hydrolyzed (partially hydrolysed products). It may be a thing). That is, the above-mentioned hydrolyzate may be a complete hydrolyzate, a partial hydrolyzate, or a mixture thereof. Note that the details of the hydrolyzed condensate of the hydrolyzable compound are as described above, so the explanation thereof will be omitted.
  • the content of the hydrolyzable compounds is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 5.0% by mass, based on the total mass of the silica film-forming composition.
  • antioxidant Specific examples and preferred embodiments of the antioxidant are as described above, so their explanation will be omitted.
  • the content of the antioxidant is preferably 0.0005 to 2.0% by mass, more preferably 0.02 to 0.2% by mass, based on the total mass of the silica film-forming composition.
  • the composition for forming a silica film contains silica particles.
  • Specific examples and preferred embodiments of the silica particles are as described above, so their explanation will be omitted.
  • the content of silica particles is preferably 0.05 to 10.0% by mass, more preferably 0.1 to 1.0% by mass, based on the total mass of the silica film-forming composition.
  • the composition for forming a silica film preferably contains a liquid medium.
  • the liquid medium is preferably a solvent that dissolves or disperses the hydrolyzable compounds and, if necessary, disperses the silica particles used in the composition.
  • liquid medium examples include organic solvents such as alcohols, ketones, ethers, cellosolves, esters, glycol ethers, nitrogen-containing compounds, and sulfur-containing compounds, and water.
  • alcohols include methanol, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, and diacetone alcohol.
  • ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
  • ethers include tetrahydrofuran and 1,4-dioxane.
  • cellosolves include methyl cellosolve, ethyl cellosolve, and butyl cellosolve.
  • esters include methyl acetate, ethyl acetate, and butyl acetate.
  • glycol ethers include ethylene glycol monoalkyl ether.
  • nitrogen-containing compounds include N,N-dimethylacetamide, N,N-dimethylformamide, and N-methylpyrrolidone.
  • a specific example of the sulfur-containing compound is dimethyl sulfoxide.
  • the liquid medium may be used alone or in combination of two or more.
  • the liquid medium preferably contains only water or is a mixed solvent of water and an organic solvent.
  • the organic solvent is preferably an alcohol, particularly isopropanol or a mixed alcohol (for example, Solmix AP-11 (manufactured by Nippon Alcohol Sales Co., Ltd.)).
  • an antioxidant it is preferable to dissolve the antioxidant in advance in butyl acetate or acetone, in which the antioxidant has good solubility.
  • the content of the liquid medium is preferably 70.0 to 99.5% by mass, and 88.5 to 99% by mass based on the total mass of the composition for forming a silica film. .0% by mass is more preferable.
  • the composition for forming a silica film may contain other components than those mentioned above.
  • specific examples of other components include metal catalysts, acid catalysts (for example, nitric acid), silicone oils, surfactants, pH adjusters, and antifoaming agents, among which it is preferable to use acid catalysts.
  • the content of the other components is preferably 0.1 to 20% by mass, and 0.5% by mass based on the total mass of the composition for forming a silica film. More preferably 10% by mass.
  • the content of the acid catalyst is determined based on the total mass of the composition for forming a silica film, from the viewpoint of controllability of hydrolysis and condensation of hydrolyzable compounds. It is preferably 0.0001 to 5.0% by weight, more preferably 0.001 to 3.0% by weight.
  • the composition for forming a silica film can be produced by mixing hydrolyzable compounds, an antioxidant, and optional components (for example, silica particles, a liquid medium, and an acid catalyst).
  • hydrolyzable compounds for example, silica particles, a liquid medium, and an acid catalyst.
  • optional components for example, silica particles, a liquid medium, and an acid catalyst.
  • the resulting sol-gel solution, an antioxidant, and optional components may be mixed to produce the sol-gel solution.
  • Application methods include spin coating, spray coating, dip coating, die coating, curtain coating, screen coating, inkjet coating, flow coating, gravure coating, bar coating, flexo coating, and slit coating. , a wet coating method such as a roll coating method.
  • Drying may be performed by heating, or may be performed by natural drying or air drying without heating.
  • the drying temperature is preferably 50°C to 400°C, more preferably 100°C to 350°C, and even more preferably 200 to 300°C, in view of the excellent hardness of the silica film.
  • the drying time may be appropriately set depending on the drying temperature, the size of the substrate, etc., but is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 90 minutes, and even more preferably 30 minutes to 60 minutes.
  • ⁇ Other processes> When it is desired to obtain a substrate 1A with a silica film including the above-mentioned intermediate layer between the substrate 10 and the silica film 20, an intermediate layer is formed on the surface of the substrate 10 before applying the composition for forming a silica film on the substrate 10.
  • the method may further include a step of applying a layer-forming composition to form an intermediate layer.
  • the silica film-forming composition is applied to the surface of the intermediate layer formed on the substrate 10.
  • the intermediate layer forming composition preferably contains a silane coupling agent and a liquid medium, and may also contain a catalyst. Specific examples and preferred embodiments of the silane coupling agent are as described above, so their explanation will be omitted.
  • the content of the silane coupling agent is preferably 0.1 to 5.0% by mass, more preferably 0.3 to 3.0% by mass, based on the total mass of the intermediate layer forming composition.
  • the specific example of the liquid medium in the composition for forming an intermediate layer is the same as the specific example of the liquid medium that can be included in the composition for forming a silica film, so a description thereof will be omitted.
  • the content of the liquid medium is preferably 95.0 to 99.9% by mass, more preferably 97.0 to 99.7% by mass, based on the total mass of the intermediate layer forming composition.
  • the specific example of the method for applying the composition for forming an intermediate layer is the same as the specific example of the method for applying the composition for forming a silica film, so the explanation thereof will be omitted.
  • the step of forming the intermediate layer may include a process of drying the intermediate layer forming composition applied to the substrate 10.
  • Specific examples of the drying conditions for the composition for forming an intermediate layer applied to the substrate 10 are the same as those for the composition for forming a silica film applied to the substrate 10 described above, so the explanation thereof will be omitted.
  • Examples 1-1 to 1-23 and 2-1 are examples, and examples 1-24 to 1-29 and 2-2 are comparative examples. However, the present invention is not limited to these examples. Note that the amounts of each component in the table described below are based on mass.
  • C/Si ratio of carbon atom content to silicon atom content in a silica film
  • XPS X-ray photoelectron spectroscopy
  • the average primary particle diameter of the silica particles was determined by taking an SEM photograph of the silica particles using a scanning electron microscope (S-4800, manufactured by Hitachi High Technologies), and measuring the major axis diameter of 100 primary particles in the image. . The arithmetic mean value was adopted as the average primary particle diameter of the silica particles.
  • silica film forming composition 1 Mix 1.43g of X-40-9246, 3.33g of methyltriethoxysilane (MTES), 2.50g of Snowtex ST-OXS, and 38.83g of Solmix AP-11 (alcohol solvent), and add pure water. After dropping 0.25 g of a 1% nitric acid aqueous solution prepared by diluting 3.67 g of 60% nitric acid aqueous solution and 0.0042 g of a 60% nitric acid aqueous solution with 0.246 g of pure water, the mixture was stirred at 60° C. for 30 minutes to obtain a concentrated liquid.
  • MTES methyltriethoxysilane
  • Solmix AP-11 alcohol solvent
  • compositions 2 to 23 A silica film was formed in the same manner as in the preparation of Composition 1 for forming a silica film, except that the amount of each component used was adjusted so that the content (parts by mass) of each component became the values listed in Tables 1 to 5. Compositions 2 to 23 were obtained.
  • Example 1-1 Silica film-forming composition 1 was applied by spin coating onto soda lime glass (manufactured by AGC, size: 10 x 10 mm, thickness: 2 mm) whose surface had been cleaned, and dried at 200° C. in the atmosphere for 30 minutes. Thus, a silica film-coated substrate of Example 1-1 was obtained.
  • Example 1-1 except that the silica film-forming composition listed in Table 1 was used instead of silica film-forming composition 1, and the coating conditions were adjusted so that the thickness of the silica film was the value shown in Table 1.
  • silica film-coated substrates of Examples 1-2 to 1-19, 1-21, and 1-24 to 1-29 were produced.
  • Intermediate layer forming composition 1 was obtained by mixing 0.11 g of KBP-90 (manufactured by Shin-Etsu Silicone Co., Ltd., an aminosilane-based silane coupling agent) and 49.9 g of 1-butanol. Intermediate layer forming composition 1 was then applied by spin coating onto soda lime glass (manufactured by AGC, size: 10 x 10 mm, thickness: 2 mm) whose surface had been cleaned, and dried at room temperature for 5 minutes. An intermediate layer (thickness: 15 nm) was formed on the surface of soda lime glass.
  • composition 1 for forming a silica film was applied to the surface of the intermediate layer by a spin coating method, and dried in the atmosphere at 200°C for 30 minutes to form an intermediate layer between the soda lime glass and the silica film
  • Example 1 A substrate with a silica film of -17 was obtained.
  • Example 1-22 Silica film-forming composition 1 was applied by spin coating onto soda lime glass (manufactured by AGC, size: 10 x 10 mm, thickness: 2 mm) whose surface had been cleaned, and dried at 300° C. for 60 minutes in the air. Thus, a silica film-coated substrate of Example 1-22 was obtained.
  • Example 1-23 A substrate with a silica film of Example 1-23 was prepared in the same manner as Example 1-22 except that the coating conditions were adjusted so that the thickness of the silica film was as shown in Table 1.
  • Example 2-1 A silica film-coated substrate of Example 2-1 was obtained in the same manner as Example 1-1, except that an aluminum substrate (size: 100 x 100 mm, thickness: 4.0 mm) was used instead of soda lime glass as the substrate. Ta.
  • Example 2-2 A substrate with a silica film of Example 2-2 was produced in the same manner as Example 2-1 except that Composition 22 for forming a silica film was used instead of Composition 1 for forming a silica film.
  • the silica film contains a hydrolyzed condensate of a hydrolyzable compound including the compound represented by formula (1) above, and an antioxidant, and the antioxidant content is the same as that of the silica film.
  • the silica film that is 25% by mass or less based on the mass, has a C/Si of 0.90 or more, and has a thickness of 15 nm or more, the silica film has excellent initial oil repellency and oil repellency after heating at 300°C. It was confirmed that a bonded substrate could be obtained.
  • the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2022-123895 filed on August 3, 2022 are cited here, and as a disclosure of the specification of the present invention, It is something to be taken in.

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Abstract

La présente invention concerne un substrat avec un film de silice, qui a un excellent caractère oléofuge initial, tout en ayant un caractère oléofuge amélioré après avoir été chauffé à 300°C.Un substrat avec un film de silice selon la présente invention comprend un substrat et un film de silice qui est disposé sur le substrat ; le film de silice contient un antioxydant et un produit de condensation par hydrolyse d'un composé hydrolysable qui contient un composé représenté par Si(-R1)n(-OR2)4-n ; la teneur de l'antioxydant est de 25 % en masse ou moins par rapport à la masse totale du film de silice ; et le rapport de la teneur en atomes de carbone à la teneur en atomes de silicium dans le film de silice est de 0,90 ou plus ; et l'épaisseur du film de silice est de 15 nm ou plus. Dans la formule, R1 représente un groupe alkyle ayant 1 à 3 atomes de carbone ; R2 représente un groupe méthyle ou un groupe éthyle ; et n représente un nombre entier de 1 à 3.
PCT/JP2023/028164 2022-08-03 2023-08-01 Substrat doté d'un film de silice WO2024029537A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09194731A (ja) * 1996-01-23 1997-07-29 Asahi Glass Co Ltd 硬化性組成物
JPH1149970A (ja) * 1997-07-31 1999-02-23 Asahi Glass Co Ltd 室温硬化性の組成物
JP2000129145A (ja) * 1998-10-22 2000-05-09 Asahi Glass Co Ltd 室温硬化性の組成物
JP2010197559A (ja) * 2009-02-24 2010-09-09 Konica Minolta Opto Inc 反射防止層用組成物、反射防止フィルム、偏光板、及び画像表示装置
WO2018070426A1 (fr) * 2016-10-12 2018-04-19 日産化学工業株式会社 Stratifié de couche dure anti-éblouissement
WO2019035271A1 (fr) * 2017-08-17 2019-02-21 信越化学工業株式会社 Élément hydrofuge, et procédé de fabrication de celui-ci
JP2021160225A (ja) * 2020-03-31 2021-10-11 マツダ株式会社 積層体およびその製造方法ならびに吸湿膜形成用塗料組成物

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09194731A (ja) * 1996-01-23 1997-07-29 Asahi Glass Co Ltd 硬化性組成物
JPH1149970A (ja) * 1997-07-31 1999-02-23 Asahi Glass Co Ltd 室温硬化性の組成物
JP2000129145A (ja) * 1998-10-22 2000-05-09 Asahi Glass Co Ltd 室温硬化性の組成物
JP2010197559A (ja) * 2009-02-24 2010-09-09 Konica Minolta Opto Inc 反射防止層用組成物、反射防止フィルム、偏光板、及び画像表示装置
WO2018070426A1 (fr) * 2016-10-12 2018-04-19 日産化学工業株式会社 Stratifié de couche dure anti-éblouissement
WO2019035271A1 (fr) * 2017-08-17 2019-02-21 信越化学工業株式会社 Élément hydrofuge, et procédé de fabrication de celui-ci
JP2021160225A (ja) * 2020-03-31 2021-10-11 マツダ株式会社 積層体およびその製造方法ならびに吸湿膜形成用塗料組成物

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