WO2022059353A1 - Substrat doté d'un film de silice - Google Patents
Substrat doté d'un film de silice Download PDFInfo
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- WO2022059353A1 WO2022059353A1 PCT/JP2021/027986 JP2021027986W WO2022059353A1 WO 2022059353 A1 WO2022059353 A1 WO 2022059353A1 JP 2021027986 W JP2021027986 W JP 2021027986W WO 2022059353 A1 WO2022059353 A1 WO 2022059353A1
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- substrate
- silica film
- mass
- silica
- film
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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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
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
- B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
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- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/10—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
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- 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.
- a method of forming a film on the surface of a substrate is known for the purpose of protecting the substrate and imparting a desired function.
- a coating liquid 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-repellent oil-repellent film on the substrate.
- the present inventors have selected the composition for forming a silica film used for forming a silica film from the group consisting of a hydrolyzable compound, a hydrolyzate thereof, and a hydrolyzed condensate thereof. If the hydrolyzable compound contains methyltrialkoxysilane and dimethyldialkoxysilane, and the thickness of the silica film is 30 nm to 120 nm, the hydrolyzable compound contains at least one compound A and silica particles. We have found that a substrate with a silica film having excellent wear resistance, scratch resistance, and oil repellency when heated can be obtained, and have reached the present invention.
- a substrate with a silica film comprising a substrate made of a glass substrate or a metal substrate, and a silica film arranged on the substrate and formed by using a composition for forming a silica film.
- the thickness of the silica film is 30 nm to 120 nm.
- the composition for forming a silica film contains at least one compound A selected from the group consisting of a hydrolyzable compound, a hydrolyzate thereof, and a hydrolyzed condensate thereof, and silica particles.
- the mass derived from the methyltrialkoxysilane in the mass obtained when it is assumed that the compound A is completely hydrolyzed and condensed is defined as the mass X
- the mass derived from the dimethyldialkoxysilane is defined as the mass Y.
- the mass of the silica particles in the silica film forming composition is the mass Z
- the hydrolyzable compound comprises only methyltrialkoxysilane and dimethyldialkoxysilane.
- the composition for forming a silica film contains the hydrolyzed condensate of the methyltrialkoxysilane and the dimethyldialkoxysilane, and the methyltrialkoxysilane as the hydrolyzable compound [1].
- a first conductive film is contained between the substrate and the silica film, and the first conductive film contains a metal oxide layer and does not contain a metal layer, [1] to [8].
- a second conductive film is contained between the substrate and the silica film, and the second dielectric film has a derivative layer, a metal layer, and a protective layer in this order from the substrate side [1].
- An oven door in which the substrate with a silica film according to any one of [1] to [10] above is provided so as to face the inner surface of the oven.
- a compound A which is at least one selected from the group consisting of a hydrolyzable compound, a hydrolyzate thereof, and a hydrolyzed condensate thereof, and silica particles are contained.
- a composition for forming a silica film, wherein the hydrolyzable compound contains methyltrialkoxysilane and dimethyldialkoxysilane.
- the present invention it is possible to provide a substrate with a silica film having excellent wear resistance, scratch resistance and oil repellency when heated.
- FIG. 1 is a cross-sectional view schematically showing an example of the substrate with a silica film of the present invention.
- the meanings of the terms in the present invention are as follows.
- the numerical range represented by using “-” means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
- the substrate with a silica film of the present invention has a substrate made of a glass substrate or a metal substrate, and a silica film arranged on the substrate and formed by using a composition for forming a silica film.
- the thickness of the silica film is 30 nm to 120 nm.
- the composition for forming a silica film contains at least one compound A selected from the group consisting of a hydrolyzable compound, a hydrolyzate thereof, and a hydrolyzed condensate thereof, and silica particles. ..
- the hydrolyzable compound also contains methyltrialkoxysilane and dimethyldialkoxysilane.
- the substrate with a silica film of the present invention is excellent in abrasion resistance, scratch resistance and oil repellency when heated. The details of this reason have not been clarified, but it is presumed that it is due to the following reasons.
- the silica film in the present invention contains at least a unit based on methyltrialkoxysilane and a unit based on dimethyldialkoxysilane, it contains a large amount of methyl groups. As a result, it is presumed that the oil-repellent effect of the methyl group could be sufficiently maintained even when the substrate with the silica film was heated. Further, the silica film in the present invention contains silica particles. As a result, it is presumed that the wear resistance is improved because the hardness of the film is increased. Further, although the reason is not clear, since the thickness of the silica film in the present invention is within the above range, the film does not deform or peel off while maintaining the methyl group density required for the development of oil repellency. It is presumed that the scratch resistance was improved by achieving the appropriate elastic modulus of.
- FIG. 1 is a cross-sectional view schematically showing an example of the substrate with a silica film of the present invention.
- the substrate 1A with a silica film has 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 surface of the substrate 10, but the present invention is not limited to this, and the silica film 20 may be formed only on a part of the region of the substrate 10. ..
- the silica film 20 is formed on only one surface 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.
- FIG. 1 is a cross-sectional view schematically showing an example of the substrate with a silica film of the present invention.
- the substrate 1A with a silica film has 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 surface of the substrate 10,
- the silica film 20 is directly formed on the upper surface of the substrate 10, but the present invention is not limited to this, and a first conductive film may be included between the substrate 10 and the silica film 20.
- the first conductive film may include a metal oxide layer and may not contain the metal layer.
- a second conductive film may be contained between the substrate 10 and the silica film 20, and the second conductive film may have a derivative layer, a metal layer, and a protective layer in this order from the substrate side. good.
- each member of the substrate 1A with a silica film will be described.
- the substrate 10 is a glass substrate or a metal substrate.
- the material constituting the glass substrate include soda lime glass, aluminosilicate glass, lithium glass, and borosilicate glass.
- the glass substrate may be chemically tempered glass.
- the glass substrate may be a glass plate having a smooth surface formed by a float method or the like, a template glass plate having irregularities on the surface, or a glass plate having a curved surface shape.
- Specific examples of the 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 intended use, and is not particularly limited, but is preferably 0.1 mm to 50 mm.
- the thickness of the glass substrate is preferably 1 mm to 10 mm, particularly preferably 1 mm to 5 mm.
- the thickness of the metal substrate is preferably 0.1 mm to 50 mm, and particularly preferably 1 mm to 10 mm.
- the silica film 20 is formed by using the composition for forming a silica film described later, and contains at least a hydrolyzed condensate of a hydrolyzable compound contained in the composition for forming a silica film and silica particles.
- the thickness of the silica film 20 is 30 nm to 120 nm, preferably 30 nm to 100 nm, and particularly preferably 30 nm to 50 nm.
- the thickness of the silica film 20 is 30 nm or more, the initial oil repellency of the substrate 1A with the silica film and the oil repellency at the time of heating are more excellent.
- the thickness of the silica film 20 is 120 nm or less, at least one of the scratch resistance and the appearance characteristics of the substrate 1A with the silica film is more excellent.
- excellent in appearance characteristics means that each component constituting the silica film is uniformly dissolved or dispersed, and the appearance is excellent, and the transparency of the silica film is excellent.
- the thickness of the silica film 20 is calculated based on an image obtained by observing a cross section of a substrate with a silica film with a scanning electron microscope (SEM).
- the silica film 20 include a protective film (for example, a scratch prevention film and an antifouling film) of a glass substrate or a metal substrate.
- a protective film for example, a scratch prevention film and an antifouling film
- composition for forming a silica film contains compound A and silica particles.
- the compound A is at least one selected from the group consisting of a hydrolyzable compound, a hydrolyzate thereof, and a hydrolyzed condensate thereof. Further, the hydrolyzable compound contains methyltrialkoxysilane and dimethyldialkoxysilane, and the hydrolyzable compound comprises only methyltrialkoxysilane and dimethyldialkoxysilane because the effect of the present invention is more excellent. Is preferable.
- compound A contained in the composition for forming a silica film is selected from the group consisting of methyltrialkoxysilane, a hydrolyzate of methyltrialkoxysilane, and a hydrolyzed condensate obtained by using methyltrialkoxysilane.
- At least one compound selected from the group consisting of dimethyldialkoxysilane, a hydrolyzate of dimethyldialkoxysilane, and a hydrolyzed condensate obtained by using dimethyldialkoxysilane. include.
- the compound A contains a hydrolyzed condensate of methyltrialkoxysilane and dimethyldialkoxysilane, only one of the hydrolyzed condensates is contained in the composition for forming a silica film. May be good.
- the composition for forming a silica film preferably contains a hydrolyzed condensate of methyltrialkoxysilane and dimethyldialkoxysilane, and methyltrialkoxysilane as a hydrolyzable compound.
- methyltrialkoxysilane which is a hydrolyzable compound
- examples of the methyltrialkoxysilane which is a hydrolyzable compound include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, and methyltributoxysilane, which are excellent in reactivity.
- Methyltriethoxysilane is preferred.
- Methyltrialkoxysilane may be used alone or in combination of two or more.
- hydrolyzable compound dimethyldialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, and dimethyldibutoxysilane, which are excellent in reactivity, and thus dimethyldimethoxysilane and dimethyl.
- Diethoxysilane is preferred.
- the dimethyldialkoxysilane may be used alone or in combination of two or more.
- the hydrolyzate of the hydrolyzable compound is intended to be a compound obtained by hydrolyzing a hydrolyzable group in the hydrolyzable compound.
- the above hydrolyzed product is one in which all of the hydrolyzable groups are hydrolyzed (completely hydrolyzed product), but a part of the hydrolyzable groups is hydrolyzed (partially hydrolyzed). It may be a thing). That is, the hydrolyzate may be a complete hydrolyzate, a partial hydrolyzate, or a mixture thereof.
- the hydrolyzed condensate of the hydrolyzable compound is intended to be a compound obtained by hydrolyzing a hydrolyzable group in the hydrolyzable compound and condensing the obtained hydrolyzate.
- the hydrolyzed condensate may be partially hydrolyzed even if all hydrolyzable groups are hydrolyzed and all the hydrolyzated products are condensed (completely hydrolyzed condensate).
- the sex group may be hydrolyzed and a part of the hydrolyzate may be condensed (partially hydrolyzed condensate). That is, the hydrolyzed condensate may be a completely hydrolyzed condensate, a partially hydrolyzed condensate, or a mixture thereof.
- the hydrolyzed condensate may be a hydrolyzed condensate obtained by condensing hydrolyzates of two or more kinds of compounds of compound A with each other.
- the composition for forming a silica film preferably contains substantially no tetraalkoxysilane from the viewpoint that the initial oil repellency of the substrate with the silica film and the oil repellency at the time of heating are more excellent.
- the fact that the composition for forming a silica film does not substantially contain tetraalkoxysilane means that the content of tetraalkoxysilane is based on 100 parts by mass of the total content of compound A and silica particles in the composition for forming a silica film. Means that is 0.1 part by mass or less, more preferably 0.01 part by mass or less, and particularly preferably 0 part by mass.
- the silica particles are particles containing silica (SiO 2 ). Specific examples of the shape of the silica particles include a spherical shape, an elliptical shape, a needle shape, a plate shape, a rod shape, a cone shape, a columnar shape, a cube shape, a rectangular parallelepiped shape, a diamond shape, a star shape, and an indefinite shape.
- the silica particles may be solid particles, hollow particles, or porous particles.
- solid particle is meant a particle that does not have a cavity inside.
- Hollow particle means a particle having a cavity inside.
- porous particle is meant a particle having a plurality of pores on its surface.
- the silica particles may exist in an independent state, the particles may be connected in a chain, or the particles 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 particularly 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 particularly preferably 1 nm or more, from the viewpoint of excellent dispersibility in the film.
- the average primary particle size of the silica particles is determined by taking an SEM photograph of the particles using a scanning electron microscope (SEM) (for example, a device equivalent to S-4800 manufactured by Hitachi High-Technologies), and the major axis of the primary particles in the image. It is a value obtained by measuring 100 diameter particles and performing arithmetic averaging.
- the major axis diameter of the primary particle in the image means the longest line segment when a straight line is drawn from one end to the other in the primary particle in the image.
- silica particles a commercially available product may be used, and examples thereof include the Snowtex series manufactured by Nissan Chemical Industries, Ltd.
- the silica particles may be used alone or in combination of two or more.
- the composition for forming a silica film preferably contains a liquid medium.
- the liquid medium is preferably a solvent that dissolves or disperses compound A and disperses silica particles 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 and ethyl acetate.
- glycol ethers include ethylene glycol monoalkyl ethers.
- nitrogen-containing compound include N, N-dimethylacetamide, N, N-dimethylformamide, and N-methylpyrrolidone.
- sulfur-containing compound include 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 from the viewpoint of hydrolyzing the hydrolyzable compound.
- a mixed solvent of water and an organic solvent is used, alcohols are preferable as the organic solvent.
- composition for forming a silica film may contain components other than the above.
- specific examples of other components include metal catalysts, silicone oils, surfactants, pH regulators (eg, acids, alkalis, etc.) and defoamers.
- the mass derived from methyltrialkoxysilane in the mass (mass of the completely hydrolyzed condensate) obtained when compound A is assumed to be completely hydrolyzed and condensed is defined as mass X
- the mass derived from dimethyldialkoxysilane is defined as mass.
- the ratio (Y / X) of the mass Y to the mass X is preferably 0.1 to 4.0.
- the ratio (Y / X) is 0.1 or more, the initial oil repellency of the silica film and the oil repellency at the time of heating are more excellent.
- the ratio (Y / X) is 4.0 or less, the abrasion resistance of the silica film is more excellent.
- the upper limit of the above ratio (Y / X) is more preferably 1 or less, and particularly preferably 0.5 or less, from the viewpoint of better wear resistance. Further, the lower limit of the ratio (Y / X) is more preferably 0.12 or more, and particularly preferably 0.15 or more, from the viewpoint that the initial oil repellency and the oil repellency at the time of heating are more excellent.
- the mass derived from methyltrialkoxysilane in the mass obtained when compound A is completely hydrolyzed and condensed means the complete hydrolysis of methyltrialkoxysilane contained as a hydrolyzable compound.
- the mass of the condensate, the mass of the completely hydrolyzed condensate of the hydrolyzate of methyltrialkoxysilane contained as the hydrolyzate, and the hydrolyzed condensate obtained by using the methyltrialkoxysilane contained as the hydrolyzed condensate. Means the sum of the mass of the unit derived from methyltrialkoxysilane in the fully hydrolyzed condensate when the above is made into a completely hydrolyzed condensate.
- the mass derived from dimethyldialkoxysilane in the mass obtained when compound A is completely hydrolyzed and condensed means that dimethyldialkoxysilane contained as a hydrolyzable compound is completely hydrolyzed and condensed.
- the mass X is the hydrolytic condensation described above.
- the mass Y corresponds to the mass derived from dimethyldialkoxysilane in the completely hydrolyzed condensate when the above hydrolyzed condensate is used as the completely hydrolyzed condensate.
- the ratio [(X + Y) / Z] of the total mass of the mass X and the mass Y to the mass Z is 2.3 to 32.3. Is preferable, 2.5 to 25 is more preferable, and 3 to 20 is particularly preferable.
- the above ratio [(X + Y) / Z] is 2.3 or more, the initial oil repellency of the silica film, the oil repellency at the time of heating, and the appearance characteristics are more excellent.
- the ratio [(X + Y) / Z] is 32.3 or less, the abrasion resistance of the silica film is more excellent.
- the content of the liquid medium is preferably 70.0 to 99.5% by mass, preferably 88.5 to 99% by mass, based on the total mass of the silica film forming composition. .0% by mass is particularly preferable.
- the content of the other components is preferably 0.1 to 20% by mass, preferably 0.5, based on the total mass of the silica film-forming composition. -10% by mass is particularly preferable.
- the composition for forming a silica film can be produced by mixing compound A, silica particles and an optional component (for example, a liquid medium). For example, after preparing a sol-gel solution of compound A, the obtained sol-gel solution and silica particles may be mixed and produced.
- the substrate with a silica film of the present invention may further have a conductive film between the substrate and the silica film.
- the conductive film may be a conductive film (first conductive film) containing a metal oxide layer and not containing a metal layer, and the dielectric layer, the metal layer, and the protective layer are formed from the substrate side. It may be a conductive film (second conductive film) included in order.
- the substrate with a silica film of the present invention may have both a first conductive film and a second conductive film between the substrate and the silica film.
- the first conductive film By having the first conductive film, it is possible to achieve both heat ray reflectivity at the time of heating and heat ray deterioration resistance.
- the heat ray deterioration resistance of the first conductive film is superior to that of the second conductive film.
- Specific examples of the material used for the metal oxide layer in the first conductive film include tin oxide and zinc tin oxide.
- the tin oxide and zinc tinate may contain a fluorine atom, an antimony atom and an indium atom. Further, since the first conductive film does not contain a metal layer, it is excellent in heat ray deterioration resistance.
- the thickness of the first conductive film is preferably 10 nm to 100 nm.
- the material used for the dielectric layer in the second conductive film include silicon oxide, silicon nitride, and silicon nitride aluminum.
- Specific examples of the material used for the metal layer in the second conductive film include silver, an alloy of silver and gold, an alloy of silver and nickel, and an alloy of silver and lead.
- Specific examples of the material used for the protective film in the second conductive film include an alloy of nickel and chromium.
- the thickness of the second conductive film is preferably 15 nm to 100 nm.
- the use of the substrate 1A with a silica film is not particularly limited, but from the viewpoint of excellent oil repellency during heating, antifouling members and kitchen members used for the inner surface of cooking utensils (for example, ovens, microwave ovens, grills). It is suitable for antifouling members used on the surface of (for example, stoves and tiles).
- the substrate 1A with a silica film is provided in the oven door so as to face the inner surface of the oven.
- Examples of the method for manufacturing the substrate 1A with a silica film include a method of applying the above-mentioned composition for forming a silica film on the substrate 10 and drying it if necessary to form the silica film 20 on the substrate 10.
- spin coat method spin coat method, spray coat method, dip coat method, die coat method, curtain coat method, screen coat method, inkjet method, flow coat method, gravure coat method, bar coat method, flexo coat method, slit coat method.
- Wet coat method such as roll coat method.
- the drying may be carried out by heating, or may be carried out by natural drying or air drying without heating.
- the drying temperature is preferably 50 ° C. or higher, and particularly preferably 100 ° C. or higher, from the viewpoint of excellent hardness of the silica film.
- the drying time may be appropriately set depending on the drying temperature, the size of the substrate, and the like, but is preferably 5 minutes or longer, and particularly preferably 10 minutes or longer.
- Examples 1 to 3 and Examples 13 to 19 are examples, and Examples 4 to 12 are comparative examples. However, the present invention is not limited to these examples.
- Average primary particle size For the average primary particle diameter of the silica particles, a scanning electron microscope (S-4800 manufactured by Hitachi High-Technologies Corporation) was used to take an SEM photograph of the silica particles, and 100 major axis diameters of the primary particles in the image were measured. .. The arithmetic mean value was adopted as the average primary particle diameter of the silica particles.
- the haze value (%) was measured by a method conforming to JIS K7136: 2000 using a haze meter (HM-65W, manufactured by Murakami Color Research Institute).
- X40-9246 A condensate of Shin-Etsu Chemical Co., Ltd., consisting of 50 mol% dimethyldimethoxysilane and 50 mol% methyltrimethoxysilane, having an average molecular weight of 870 [hydrolyzable compound].
- -Methyltriethoxysilane manufactured by Tokyo Chemical Industry Co., Ltd.
- -Dimethyldimethoxysilane manufactured by Tokyo Chemical Industry Co., Ltd.
- [silica particles] -Snowtex ST-OXS Manufactured by Nissan Chemical Industries, Ltd., water-dispersed colloidal silica with an average primary particle diameter of 5 nm and a solid content of 10% by mass.
- composition 1 for forming a silica film While stirring 76.5 g of Solmix AP-11, add 3 g of X40-9246 and 7 g of methyltriethoxysilane, then add 13 g of water and 0.5 g of 1% by mass of nitrate to adjust the pH of the solution. The pH was adjusted to 3 and stirred at 60 ° C. for 30 minutes to obtain 100 g of a sol-gel solution (solid content concentration: 10% by mass).
- compositions 2 to 12 for Forming Silica Film The amount (g) of the hydrolyzed condensate (X40-9246), the hydrolyzable compound (methyltriethoxysilane), and the silica particles (Snowtex ST-OXS) is set to the values shown in Table 1. , The amount of each component charged was adjusted to obtain compositions 2 to 12 for forming a silica film.
- composition 14 for forming a silica film While stirring 75.9 g of Solmix AP-11, 2 g of X40-9246, 4 g of methyltriethoxysilane and 4 g of dimethyldimethoxysilane were added, followed by 13.6 g of water and 1% by mass of nitrate. 5 g was added, the pH of the solution was adjusted to 3, and the mixture was stirred at 60 ° C. for 30 minutes to obtain 100 g of a solgel solution (solid content concentration: 10% by mass).
- Example 1 The composition 1 for forming a silica film is applied to a soda lime glass (made by AGC, size: 10 ⁇ 10 mm, thickness: 2 mm) whose surface has been washed by a spin coating method, and dried in the air at 200 ° C. for 30 minutes. The substrate with the silica film of Example 1 was obtained.
- a soda lime glass made by AGC, size: 10 ⁇ 10 mm, thickness: 2 mm
- Examples 2 to 12 The same as in Example 1 except that the silica film forming composition shown in Table 1 was used instead of the silica film forming composition 1 and the coating conditions were adjusted so that the thickness of the silica film became the value shown in Table 1. Then, the substrates with the silica film of Examples 2 to 12 were produced.
- Examples 13 to 19 The same as in Example 1 except that the silica film forming composition shown in Table 2 was used instead of the silica film forming composition 1 and the coating conditions were adjusted so that the thickness of the silica film became the value shown in Table 2. Then, the substrates with the silica film of Examples 13 to 19 were produced.
- the mass Z means the mass (g) of the silica particles in the composition for forming a silica film.
- Y / X means the ratio of the mass Y to the mass X
- (X + Y) / Z means the ratio of the total mass of the mass X and the mass Y to the mass Z.
- “>5,000” means that the hardness is larger than 5,000
- “ ⁇ H” means that the hardness is lower than that of H.
- D means that the evaluation has not been performed.
- the composition for forming a silica film used for forming a silica film is at least one selected from the group consisting of a hydrolyzable compound, a hydrolyzate thereof, and a hydrolyzed condensate thereof. If the hydrolyzable compound contains methyltrialkoxysilane and dimethyldialkoxysilane and the thickness of the silica film is 30 nm to 120 nm, it contains abrasion resistance and scratch resistance. It was confirmed that a substrate with a silica film having excellent properties and oil repellency during heating could be obtained (Examples 1 to 3 and Examples 13 to 19).
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Abstract
Un substrat doté d'un film de silice selon la présente invention comprend un substrat comprenant un substrat de verre ou un substrat métallique et un film de silice agencé sur le substrat et formé à l'aide d'une composition de formation de film de silice, dans lequel l'épaisseur du film de silice est de 30 nm à 120 nm, la composition de formation de film de silice comprend au moins un composé A choisi dans le groupe constitué par un composé hydrolysable, un produit d'hydrolyse associé et un produit de condensation d'hydrolyse associé et des particules de silice et le composé hydrolysable comprend du méthyltrialcoxysilane et du diméthyldialcoxysilane.
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JP2022550395A JPWO2022059353A1 (fr) | 2020-09-18 | 2021-07-28 |
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JP2020-157580 | 2020-09-18 | ||
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WO2022059353A1 true WO2022059353A1 (fr) | 2022-03-24 |
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PCT/JP2021/027986 WO2022059353A1 (fr) | 2020-09-18 | 2021-07-28 | Substrat doté d'un film de silice |
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WO (1) | WO2022059353A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024204213A1 (fr) * | 2023-03-29 | 2024-10-03 | 日本電気硝子株式会社 | Plaque supérieure pour dispositif de cuisson et procédé de production associé et procédé d'évaluation de carbonisation |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000081214A (ja) * | 1998-07-02 | 2000-03-21 | Matsushita Electric Ind Co Ltd | オ―ブンレンジおよびその汚れ防止方法 |
WO2009022583A1 (fr) * | 2007-08-10 | 2009-02-19 | Ulvac, Inc. | Composition de précurseur de silice poreuse et son procédé de préparation, film de silice poreuse et son procédé de fabrication, dispositif à semi-conducteur, dispositif d'affichage d'image et écran à cristaux liquides |
JP2009053373A (ja) * | 2007-08-24 | 2009-03-12 | Panasonic Electric Works Co Ltd | 反射防止膜付き基材 |
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2021
- 2021-07-28 JP JP2022550395A patent/JPWO2022059353A1/ja active Pending
- 2021-07-28 WO PCT/JP2021/027986 patent/WO2022059353A1/fr active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000081214A (ja) * | 1998-07-02 | 2000-03-21 | Matsushita Electric Ind Co Ltd | オ―ブンレンジおよびその汚れ防止方法 |
WO2009022583A1 (fr) * | 2007-08-10 | 2009-02-19 | Ulvac, Inc. | Composition de précurseur de silice poreuse et son procédé de préparation, film de silice poreuse et son procédé de fabrication, dispositif à semi-conducteur, dispositif d'affichage d'image et écran à cristaux liquides |
JP2009053373A (ja) * | 2007-08-24 | 2009-03-12 | Panasonic Electric Works Co Ltd | 反射防止膜付き基材 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024204213A1 (fr) * | 2023-03-29 | 2024-10-03 | 日本電気硝子株式会社 | Plaque supérieure pour dispositif de cuisson et procédé de production associé et procédé d'évaluation de carbonisation |
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JPWO2022059353A1 (fr) | 2022-03-24 |
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