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WO2016051718A1 - Revêtement à faible réflexion, feuille de verre équipée de revêtement à faible réflexion, feuille de verre présentant un revêtement à faible réflexion, substrat de verre et dispositif de conversion photoélectrique - Google Patents

Revêtement à faible réflexion, feuille de verre équipée de revêtement à faible réflexion, feuille de verre présentant un revêtement à faible réflexion, substrat de verre et dispositif de conversion photoélectrique Download PDF

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Publication number
WO2016051718A1
WO2016051718A1 PCT/JP2015/004782 JP2015004782W WO2016051718A1 WO 2016051718 A1 WO2016051718 A1 WO 2016051718A1 JP 2015004782 W JP2015004782 W JP 2015004782W WO 2016051718 A1 WO2016051718 A1 WO 2016051718A1
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WIPO (PCT)
Prior art keywords
reflection coating
low
fine particles
low reflection
silica fine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/004782
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English (en)
Japanese (ja)
Inventor
瑞穂 小用
竜一 田代
河津　光宏
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Nippon Sheet Glass Co Ltd
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Nippon Sheet Glass Co Ltd
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Publication date
Application filed by Nippon Sheet Glass Co Ltd filed Critical Nippon Sheet Glass Co Ltd
Priority to JP2016551515A priority Critical patent/JP6487933B2/ja
Publication of WO2016051718A1 publication Critical patent/WO2016051718A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • 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
    • C09D183/04—Polysiloxanes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/16—Material structures, e.g. crystalline structures, film structures or crystal plane orientations
    • H10F77/169—Thin semiconductor films on metallic or insulating substrates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a low reflection coating, a glass plate with a low reflection coating, a glass plate having a low reflection coating, a glass substrate, and a photoelectric conversion device.
  • a low reflection coating is formed on the surface of a substrate such as glass or ceramic in order to transmit more light or prevent glare due to reflection for the purpose of improving the function of the substrate.
  • Low reflection coating is used for glass for vehicle, show window or glass plate used for photoelectric conversion device.
  • a so-called thin film type solar cell which is a kind of photoelectric conversion device, uses a glass plate in which a photoelectric conversion layer and a back surface thin film electrode made of a base film, a transparent conductive film, amorphous silicon, and the like are sequentially laminated, but a low reflection coating is laminated. It is formed on the main surface opposite to the main plane, that is, the main surface on the side where sunlight enters. Thus, in the solar cell in which the low reflection coating is formed on the sunlight incident side, more sunlight is guided to the photoelectric conversion layer or the solar cell element, and the power generation amount is improved.
  • the most commonly used low-reflection coating is a dielectric film formed by vacuum deposition, sputtering, chemical vapor deposition (CVD), etc., but a fine particle-containing film containing fine particles such as silica fine particles should be used as the low-reflection coating.
  • the fine particle-containing film is formed by applying a coating liquid containing fine particles on a transparent substrate by dipping, flow coating, spraying, or the like.
  • Patent Document 1 a coating liquid containing fine particles and a binder precursor is applied to a glass plate having surface irregularities by a spray method, dried at 400 ° C. and then 610 ° C. 8
  • a cover glass for a photoelectric conversion device obtained through a baking process for a minute is disclosed.
  • the low reflection coating applied to the cover glass can improve the average transmittance of light having a wavelength of 380 to 1100 nm by at least 2.37%.
  • Patent Document 2 a sol containing tetraethoxysilane, aluminum acetylacetonate, and colloidal silica is attached to a glass plate by a dip coating method, and heat treatment is performed at 680 ° C. for 180 seconds.
  • a glass substrate coated therewith is disclosed.
  • the low reflection coating applied to the glass substrate can improve the average transmittance of light having a wavelength of 300 to 1100 nm by 2.5%.
  • Patent Document 3 includes colloidal silica having a dispersion particle size larger than the average primary particle size and a shape factor and an aspect ratio of more than 1 to some extent, tetraalkoxysilane, and aluminum nitrate.
  • a coating-coated silicon substrate obtained by applying a coating composition containing the coating composition on a silicon substrate using a spin coater and performing a drying process at 100 ° C. for 1 minute is disclosed. Although there is no description about the improvement of the average light transmittance by this film, this film has a refractive index of 1.40 or less.
  • the transmittance gain is an increase in transmittance by applying a low-reflection coating with respect to transmittance, for example, average transmittance in a predetermined wavelength range. Specifically, it is determined as a value obtained by subtracting the transmittance before applying the coating from the transmittance when the coating is applied to the substrate.
  • a photoelectric conversion device when manufacturing a photoelectric conversion device using a glass plate, a photoelectric conversion device is manufactured by using a glass plate that has been previously coated with a low reflection coating.
  • the applied low reflection coating may be unintentionally damaged or soiled in the manufacturing process of the photoelectric conversion device, or the low reflection characteristics may be deteriorated.
  • the present invention provides a low-reflection coating having a high transmittance gain, a low-reflection coating excellent in wear resistance, and a photoelectric conversion device using a glass plate not provided with the low-reflection coating. Is suitable for being applied to the surface on which light is incident on the photoelectric conversion device, and provides a low reflection coating having the above characteristics (high transmittance gain and / or excellent wear resistance). Objective.
  • the present invention provides a low reflection coating that can be suitably applied to at least one of the main surfaces of a substrate.
  • the low reflection coating is a film in which solid spherical silica fine particles are fixed by a binder mainly composed of a metal oxide,
  • the silica fine particles include silica fine particles having an average particle diameter of 200 to 600 nm,
  • the binder includes silica as a metal oxide,
  • a low-reflection coating characterized in that a transmittance gain obtained by applying the low-reflection coating to a substrate is 1.5% or more.
  • the transmittance gain is an increase in the average transmittance of the substrate having the low reflection coating with respect to the average transmittance of the substrate before the low reflection coating, with respect to the average transmittance in the wavelength region of 380 to 850 nm.
  • the low reflection coating of the present invention includes solid silica fine particles having an average particle diameter in a predetermined range and a binder mainly composed of a metal oxide, by applying the low reflection coating of the present invention to a substrate.
  • the obtained transmittance gain is 1.5% or more.
  • the low reflection coating of the present invention contains silica fine particles having an average particle size of 200 to 600 nm, the low reflection coating of the present invention has excellent wear resistance and / or high transmittance gain.
  • the first aspect of the low reflection coating of the present invention comprises a porous film in which solid spherical silica fine particles are fixed by a binder mainly composed of a metal oxide.
  • the binder may further contain an aluminum compound, and the metal oxide as the main component is preferably silica.
  • the “main component” means a component that is contained most on a mass basis.
  • the silica fine particles fixed by the binder include silica fine particles having an average particle size of 200 to 600 nm and silica fine particles having an average particle size of 80 to 150 nm, both of which are substantially spherical primary particles.
  • the silica fine particles fixed by the binder are preferably composed of silica fine particles having an average particle diameter in the two ranges. Since silica has a higher hardness than organic polymer materials and a relatively low refractive index, the apparent refractive index of a porous film composed of a binder and silica fine particles can be reduced.
  • primary particles made of silica and having a uniform particle size are produced at a low cost on a commercial scale, and are excellent in quantity, quality, and cost availability.
  • the “average particle size” is determined by observing a cross section of the low reflection coating using a scanning electron microscope SEM. Specifically, for any 50 particles that can observe the entire particle, the maximum diameter and the minimum diameter are measured, and the average value is used as the particle diameter of each particle. The average value of the particle diameters of the 50 particles is expressed as “ Determined as "average particle size”.
  • the silica fine particles having an average particle diameter of 200 to 600 nm are preferably 2 to 30 parts by mass with respect to 100 parts by mass of the total amount of silica fine particles fixed by the binder.
  • the silica fine particles having an average particle diameter of 200 to 600 nm are in the above-mentioned range, the low reflection coating has both a high transmittance gain of 1.5% or more and a high wear resistance.
  • the amount is less than 2 parts by mass, the wear resistance is deteriorated, and when the amount exceeds 30 parts by mass, the transmittance gain is decreased.
  • the aluminum compound preferably contained in the binder is preferably derived from a water-soluble inorganic aluminum compound added to a coating solution for forming a low reflection coating, and more preferably derived from aluminum halide or aluminum nitrate.
  • the preferred aluminum halide is aluminum chloride.
  • the content of the aluminum compound in the low reflection coating is 2 to 7% by mass, preferably 5 to 7% by mass, when the aluminum compound is converted to Al 2 O 3 .
  • the content of silica fine particles in the low reflection coating is 55 to 75% by mass, preferably 60 to 70% by mass, and the silica content in the binder is 25 to 45% by mass, and 30 to 40% by mass. % Is preferred.
  • the content ratio of the silica fine particles in the low reflection coating and the silica in the binder is in the range of 80:20 to 30:70, preferably in the range of 70:30 to 60:40, expressed as a mass ratio.
  • This content ratio can increase the reflectance gain of the low-reflection coating as the content ratio of the silica fine particles increases. This is because gaps between the silica fine particles and between the silica fine particles and the transparent substrate become large.
  • the content ratio of the silica fine particles is larger than the limit, the durability of the low reflective film coating is lowered.
  • silica in the binder has a function of adhering between the silica fine particles or between the silica fine particles and the transparent substrate, but if the content ratio of the silica fine particles is too large, the effect becomes poor. On the other hand, when the content ratio of the silica fine particles is smaller than the limit, the above-mentioned voids are too small, and the reflectance gain of the low reflection coating is lowered.
  • the transmittance gain obtained by applying the low reflection coating to the substrate may be 1.5% or more, preferably 2.5% or more. it can.
  • the second aspect of the low reflection coating of the present invention comprises a film in which solid spherical silica fine particles are fixed by a binder containing silica as a main component.
  • the silica fine particles fixed by the binder are composed of silica fine particles having an average particle diameter of 200 to 600 nm. Since silica has a higher hardness than organic polymer materials and a relatively low refractive index, the apparent refractive index of the porous layer composed of the binder and the silica fine particles can be further reduced.
  • primary particles made of silica and having a uniform particle size are produced at a low cost on a commercial scale, and are excellent in quantity, quality, and cost availability.
  • the binder may consist essentially of silica.
  • the term “substantially composed of silica” means that a small amount of components other than silica in the binder is allowed as long as the effect to be obtained by the present invention is not impaired. To do.
  • the silica content in the binder is 99% or more, preferably 99.5% or more, and more preferably 99.9% or more.
  • the content of silica fine particles in the low reflection coating is 55 to 70% by mass, preferably 60 to 70% by mass, and the silica content in the binder is 30 to 45% by mass, and 30 to 40% by mass. % Is preferred.
  • the content ratio of the silica fine particles in the low reflection coating and the silica in the binder is in the range of 75:25 to 30:70, preferably in the range of 70:30 to 60:40, expressed as a mass ratio.
  • This content ratio can increase the reflectance gain of the low-reflection coating as the content ratio of the silica fine particles increases. This is because gaps between the silica fine particles and between the silica fine particles and the transparent substrate become large.
  • the content ratio of the silica fine particles is larger than the limit, the durability of the low reflection coating is lowered.
  • silica in the binder has a function of adhering between the silica fine particles or between the silica fine particles and the transparent substrate, but if the content ratio of the silica fine particles is too large, the effect becomes poor. On the other hand, when the content ratio of the silica fine particles is smaller than the limit, the above-mentioned voids are too small, and the reflectance gain of the low reflection coating is lowered.
  • the transmittance gain obtained by applying the low reflection coating to the substrate may be 1.5% or more, preferably 2.5% or more.
  • high wear resistance can be obtained.
  • a third aspect of the low-reflection coating of the present invention is a film in which solid spherical silica fine particles are fixed by a binder having a refractive index of 1.5 to 1.8 at a wavelength of 550 nm. It consists of silica fine particles having an average particle diameter of 200 to 600 nm.
  • the binder contains silica as a main component.
  • the binder further includes a high refractive index component.
  • the silica fine particles are arranged on the main plane, and the binder has a diameter (average particle size) of the silica fine particles from the main plane. It exists between the main plane and the silica fine particles at a thickness of 30% to 70% of the diameter.
  • the thickness of the binder is less than 30%, the wear resistance deteriorates and the transmittance gain decreases, and when it exceeds 70%, the transmittance gain decreases rapidly.
  • Silica as fine particles has a higher hardness than organic polymer materials and a relatively low refractive index, so that the apparent refractive index of a porous layer made of a binder and silica fine particles can be reduced.
  • primary particles made of silica and having a uniform particle size are produced at a low cost on a commercial scale, and are excellent in quantity, quality, and cost availability.
  • the high refractive index component contained in the binder is preferably a compound of one or more metals selected from the group consisting of titanium, zirconium, niobium, zinc, chromium, aluminum, cadmium, strontium, yttrium, europium, and lanthanum. More preferably, they are titanium oxide, zirconium oxide, or aluminum oxide.
  • the transmittance gain obtained by applying the low reflection coating to the substrate may be 1.5% or more, preferably 2.5% or more. it can.
  • a hydrolyzable silicon compound typified by silicon alkoxide can be used as a silica source in the binder.
  • the silicon alkoxide include tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane.
  • These hydrolyzable silicon compounds may be made into binders by hydrolysis and condensation polymerization by a so-called sol-gel method.
  • the silica in the binder is derived from a hydrolyzable silicon compound or a hydrolyzate of a hydrolyzable silicon compound added to a coating solution for forming a low reflection coating.
  • the hydrolyzable silicon compound includes, for example, a compound represented by the following formula (I).
  • X is at least one selected from an alkoxyl group, an acetoxy group, an alkenyloxy group, an amino group, and a halogen atom.
  • the hydrolyzable silicon compound added to the coating solution is preferably tetraalkoxysilane.
  • Hydrolysis of the hydrolyzable silicon compound can be carried out as appropriate, but is preferably carried out in a solution containing silica fine particles.
  • it is preferable to prepare a coating liquid by sequentially adding a hydrolysis catalyst and silicon alkoxide while stirring a solution containing silica fine particles.
  • an acid and a base can be used for a hydrolysis catalyst, it is preferable to use an acid, especially an inorganic acid, and it is more preferable to use hydrochloric acid. This is because the acidity is better than the basicity, and the dispersibility of the silica fine particles is better and the stability of the coating liquid is also better. Furthermore, chlorine ions derived from hydrochloric acid increase the concentration of chlorine ions in the coating solution, and thus promote the effect brought about by the aluminum chloride added to the coating solution described above.
  • the low reflection coating of the present invention can be formed by applying a coating liquid, drying and curing.
  • a method for supplying these coating solutions any known method such as spin coating, roll coating, bar coating, dip coating, spray coating, etc. can be used, but spray coating is excellent in terms of mass productivity, Roll coating and bar coating are more suitable in terms of homogeneity of the appearance of the coating film in addition to mass production.
  • the maximum temperature experienced by the substrate is 350 ° C. or less, and the time that the substrate is at a temperature of 200 ° C. or more is 5 minutes or less. .
  • the maximum temperature experienced by the substrate is 250 ° C. or lower, and the time during which the substrate is at a temperature of 100 ° C. or higher is 2 Is less than a minute.
  • the substrate to which the low reflection coating according to the first aspect, the second aspect, or the third aspect of the present invention can be suitably applied may be an uncoated glass plate.
  • a photoelectric conversion device can be provided using this glass plate.
  • the main plane of the glass plate on which the low reflection coating is formed is the main surface on which light is incident.
  • the glass plate may be a float plate glass having a smoothness with an arithmetic average roughness Ra of the main surface of, for example, 1 nm or less, preferably 0.5 nm or less.
  • the arithmetic average roughness Ra is a value defined in JIS (Japanese Industrial Standards) B0601-1994.
  • the glass plate may be a template glass having irregularities on the surface thereof, and the average interval Sm of the irregularities is 0.3 mm or more and 2.5 mm or less, further 0.3 mm or more, particularly 0.4 mm or more, especially It is preferably 0.45 mm or more, 2.5 mm or less, more preferably 2.1 mm or less, particularly 2.0 mm or less, and particularly preferably 1.5 mm or less.
  • the average interval Sm means the average value of the intervals of one mountain and valley obtained from the point where the roughness curve intersects the average line.
  • the surface irregularities of the template glass plate preferably have a maximum height Ry of 0.5 ⁇ m to 10 ⁇ m, particularly 1 ⁇ m to 8 ⁇ m, together with the average interval Sm in the above range.
  • the average interval Sm and the maximum height Ry are values defined in JIS (Japanese Industrial Standards) B0601-1994.
  • a glass plate may be the same composition as normal plate glass and building plate glass, it is preferable that a coloring component is not included as much as possible.
  • the content of iron oxide which is a typical coloring component, is preferably 0.06% by mass or less, particularly preferably 0.02% by mass or less in terms of Fe 2 O 3 .
  • the substrate to which the low reflection coating of the first aspect, the second aspect, or the third aspect of the present invention can be suitably applied may be a glass substrate with a transparent conductive film.
  • This glass substrate with a transparent conductive film has, for example, a transparent conductive film on one main plane (a main plane opposite to the main plane on which the low-reflective coating is to be formed) of any of the glass plates described above.
  • one or more underlayers, for example, a transparent conductive layer mainly composed of fluorine-doped tin oxide may be laminated in order on the main plane of the glass plate.
  • a photoelectric conversion device using this glass substrate can be provided.
  • the main plane of the glass plate on which the low reflection coating is formed is the main surface on which light is incident.
  • the transmittance curve (transmission spectrum) of the substrate before and after the formation of the low reflection coating was measured.
  • the average transmittance was calculated by averaging the transmittance at a wavelength of 380 to 850 nm.
  • the increment of the average transmittance of the substrate with the low reflection coating with respect to the average transmittance of the substrate before the low reflection coating was defined as the transmittance gain.
  • a reciprocating wear test was performed on the substrate on which the low-reflection coating according to each example was formed and the substrate according to Comparative Example 1 using a reciprocating wear tester manufactured by Daiei Kagaku Seiki Seisakusho.
  • the substrate on which the low reflection coating according to each Example was formed and the substrate according to Comparative Example 1 were fixed with a jig.
  • the substrate on which the low reflection coating was formed with the low reflection coating side facing upward was fixed with a jig.
  • a circular surface of a disc-shaped wear piece CS-10F having a diameter of 19 mm was brought into contact with the surface of the low reflection coating or the substrate, and a load of 4N was applied.
  • the contact area between the wearer CS-10F and the surface of the low reflection coating or the substrate was 284 mm 2 .
  • the wearer CS-10F was reciprocated linearly 50 times with respect to the surface of the low reflection coating or the substrate.
  • the speed of the wearer at this time was set to 120 mm / second, and the stroke width of the wearer was set to 120 mm.
  • the peeling state of the low reflection coating was visually confirmed, and the case where there was no peeling of the low reflection coating was evaluated as “ ⁇ ”.
  • the low reflection coating according to each example and comparative example was observed using a field emission scanning electron microscope (FE-SEM) (manufactured by Hitachi, Ltd., model: S-4500). From the FE-SEM photograph of the cross section of the low-reflection coating obliquely from 30 ° above, the average value of the thickness of the low-reflection coating at five measurement points was calculated as the film thickness (average film thickness) of the low-reflection coating.
  • FE-SEM field emission scanning electron microscope
  • Example 1 ⁇ Preparation of coating solution> Silica fine particle dispersion (Quarton PL-7, substantially spherical primary particles having an average particle diameter of 125 nm, solid content concentration 23 wt%, manufactured by Fuso Chemical Industry Co., Ltd.) 55.1 parts by mass, silica fine particle dispersion (Quarton PL-20) Approximately spherical primary particles having an average particle size of 220 to 370 nm, solid content concentration of 20% by weight, manufactured by Fuso Chemical Co., Ltd.) 1.6 parts by mass, 1-methoxy-2-propanol (solvent) 18.0 parts by mass, 1 part by mass of 1N hydrochloric acid (hydrolysis catalyst) is stirred and mixed, and further, 24.3 parts by mass of tetraethoxysilane (ethyl orthosilicate, manufactured by Tama Chemical Co., Ltd.) is added while stirring, and the temperature is kept at 40 ° C.
  • tetraethoxysilane e
  • stock A the mass obtained by converting the silica fine particles to the SiO 2
  • the ratio of the mass obtained by converting the silicon oxide component contained in the binder SiO 2 is 65: A 35, average particle size 200 to silica particles per 100 parts by weight
  • the silica fine particle of ⁇ 500 nm was 2.5 parts by mass.
  • coating liquid A1 60.0 g of the above-mentioned stock solution A, 3.0 g of propylene glycol (solvent), 84.2 g of 1-methoxy-2-propanol (solvent), aluminum chloride aqueous solution (concentration 47.6% by weight as AlCl 3.
  • coating liquid A1 the solid content concentration of silicon oxide (derived from silica fine particles and tetraalkoxysilane) converted to SiO 2 is 8.0% by weight, and silicon oxide converted to SiO 2 is 100 parts by mass.
  • the aluminum compound converted to Al 2 O 3 was 5 parts by mass.
  • Example 1 the low reflective coating was formed in the main surface in which the transparent conductive film is not formed by using the glass plate with a transparent conductive film as a substrate.
  • This glass plate is composed of a normal soda lime silicate composition, and a transparent conductive film including a transparent conductive layer is formed on one main plane using an on-line CVD method. It was a glass plate. This glass plate is cut into a size of 200 mm ⁇ 300 mm, immersed in an alkaline solution (alkaline cleaning solution LBC-1, manufactured by Reybold Co., Ltd.), washed with an ultrasonic cleaner, washed with deionized water, and then at room temperature. A glass plate for drying to form a low reflection coating was obtained. When the transmission characteristics of the substrate before applying the low-reflection coating were evaluated as described above, the average transmittance was 80.0%.
  • Example 1 the coating liquid A1 was applied to the main surface of the glass plate on which the transparent conductive film was not applied, using a roll coater. At this time, the film thickness of the coating solution was adjusted to 1 to 5 ⁇ m. Next, the coating liquid applied to the glass plate was dried with hot air and cured. This hot air drying uses a belt-conveying hot-air drying device, the hot air set temperature is 300 ° C., the distance between the hot air discharge nozzle and the glass plate is set to 5 mm, and the conveying speed is set to 0.5 m / min. This was done by reciprocating the plate twice and passing under the nozzle four times.
  • the time during which the glass plate coated with the coating solution was in contact with hot air was 140 seconds, and the maximum temperature reached on the glass surface coated with the coating solution of the glass plate was 199 ° C.
  • the glass plate after drying and curing was allowed to cool to room temperature, and a low reflection coating was applied to the glass plate.
  • Example 2 ⁇ Preparation of coating solution> Silica fine particle dispersion (KE-W30, substantially spherical primary particles having an average particle diameter of 300 nm, solid concentration 20.5% by weight, manufactured by Nippon Shokubai Co., Ltd.) 63.4 parts by mass, 1-methoxy-2-propanol (solvent ) 11.3 parts by mass, 1.0 part by mass of 1N hydrochloric acid (hydrolysis catalyst) was stirred and mixed, and 24.3 parts by mass of tetraethoxysilane (same as that used in Example 1) was added while stirring. Then, the mixture was stirred for 8 hours while keeping the temperature at 40 ° C.
  • KE-W30 substantially spherical primary particles having an average particle diameter of 300 nm, solid concentration 20.5% by weight, manufactured by Nippon Shokubai Co., Ltd.
  • the ratio of the mass of silica fine particles converted to SiO 2 to the mass of silicon oxide components contained in the binder converted to SiO 2 was 65:35.
  • the above-mentioned stock solution B102.0 g and propylene glycol (solvent) 48.0 g were mixed with stirring to obtain a coating solution B1.
  • the solid content concentration obtained by converting silicon oxide (derived from silica fine particles and tetraalkoxysilane) into SiO 2 was 13.6% by weight.
  • Example 2 ⁇ Formation of low reflection film>
  • the low reflection coating was applied in the same procedure as in Example 1 except that the above-described coating liquid B1 was used, and the above-described characteristics were evaluated. The results are shown in Table 1.
  • Example 3 ⁇ Preparation of coating solution> Silica fine particle dispersion (Quatron PL-20, substantially spherical primary particles having an average particle size of 220 to 370 nm, the same as that used in Example 1) 71.2 parts by mass, 1-methoxy-2-propanol (solvent) 7 .8 parts by mass, 1.0 part by mass of 1N hydrochloric acid (hydrolysis catalyst) was mixed by stirring, and further 20.0 parts by mass of tetraethoxysilane (same as that used in Example 1) was added while stirring. Subsequently, the mixture was stirred for 8 hours while keeping the temperature at 40 ° C. to hydrolyze tetraethoxysilane to obtain a stock solution C. In Stock Solution C, the ratio of the mass of silica fine particles converted to SiO 2 to the mass of silicon oxide components contained in the binder converted to SiO 2 was 71.2: 28.8.
  • the mass ratio of the solid content concentration obtained by converting silicon oxide (derived from tetraalkoxysilane) into SiO 2 in the binder and the solid content concentration obtained by converting titanium oxide into TiO 2 was 75:25.
  • the refractive index of this binder at a wavelength of 550 nm was 1.6.
  • Example 3 ⁇ Formation of low reflection film>
  • a low-reflection coating was applied in the same procedure as in Example 1 except that the above-described coating liquid C1 was used, and the above-described characteristics were evaluated. The results are shown in Table 1.
  • Comparative Example 1 As Comparative Example 1, the same glass plate with a transparent conductive film as used in Examples 1 to 3 was used as the substrate, and the main plane on which the transparent conductive film was not formed was not subjected to the low reflection coating. Using. Prior to evaluation, it was washed and dried in the same manner as in Examples 1 to 3.
  • the low-reflective coating only by curing with hot air drying has a high transmittance gain of 1.5% or more and excellent wear resistance equivalent to the glass substrate surface before coating. I was able to get it.
  • a low-reflection coating exhibiting a high transmittance gain and / or excellent wear resistance, and preferably having a low-reflection property having such excellent characteristics even when the curing temperature is low.
  • a coating can be provided.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
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Abstract

　L'invention concerne un revêtement à faible réflexion qui peut être appliqué, de manière appropriée, sur au moins une surface principale d'un substrat. Ce revêtement à faible réflexion est un film obtenu par l'utilisation d'un liant présentant un oxyde de métal en tant que constituant principal correspondant pour immobiliser des microparticules sphériques solides de silice. Lesdites microparticules de silice comprennent des microparticules de silice présentant une taille moyenne de particule de 200-600 nm. Ledit liant comprend de la silice en tant qu'oxyde métallique. Le gain de transmittance obtenu par l'application du revêtement à faible réflexion sur un substrat est de 1,5 % ou plus. Le gain de transmittance concerne la transmittance moyenne dans une plage de longueurs d'onde de 380 à 850 nm et représente la quantité d'augmentation de la transmittance moyenne du substrat après l'application du revêtement à faible réflexion sur celui-ci par rapport à la transmittance moyenne du substrat avant l'application du revêtement à faible réflexion celui-ci.
PCT/JP2015/004782 2014-09-30 2015-09-17 Revêtement à faible réflexion, feuille de verre équipée de revêtement à faible réflexion, feuille de verre présentant un revêtement à faible réflexion, substrat de verre et dispositif de conversion photoélectrique Ceased WO2016051718A1 (fr)

Priority Applications (1)

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JP2016551515A JP6487933B2 (ja) 2014-09-30 2015-09-17 低反射コーティング、低反射コーティング付ガラス板、低反射コーティングを有するガラス板、ガラス基板、光電変換装置、及び低反射コーティングを製造する方法

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JP2014201599 2014-09-30
JP2014-201599 2014-09-30

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WO2016051718A1 true WO2016051718A1 (fr) 2016-04-07

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Cited By (2)

* Cited by examiner, † Cited by third party
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KR20230113808A (ko) 2020-12-15 2023-08-01 샌트랄 글래스 컴퍼니 리미티드 광학 부재용의 도포액, 중합체, 경화막, 감광성 도포액,패턴 경화막, 광학 부재, 고체 촬상 소자, 표시 장치, 폴리실록산 화합물, 도포액에 이용하는 안정화제, 경화막의 제조 방법, 패턴 경화막의 제조 방법, 및 중합체의 제조 방법
KR102738418B1 (ko) * 2024-08-30 2024-12-04 (주)선우이앤씨 저반사를 구현한 bipv 태양광 모듈

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WO2001047033A1 (fr) * 1999-12-20 2001-06-28 Nippon Sheet Glass Co., Ltd. Transducteur photoelectrique et substrat pour transducteur photoelectrique
WO2010134416A1 (fr) * 2009-05-22 2010-11-25 東洋紡績株式会社 Film polyester hautement adhésif à usage optique
WO2011070714A1 (fr) * 2009-12-11 2011-06-16 日本板硝子株式会社 Verre de revêtement pour convertisseur photoélectrique et procédé pour sa production
JP2014015543A (ja) * 2012-07-09 2014-01-30 Nissan Chem Ind Ltd 低屈折率コーティング組成物
JP2014032248A (ja) * 2012-08-01 2014-02-20 Nippon Sheet Glass Co Ltd 光電変換装置用カバーガラス
WO2014084093A1 (fr) * 2012-11-27 2014-06-05 共栄社化学株式会社 Composition pour revêtement dur et article moulé comportant une couche de revêtement dur

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Publication number Priority date Publication date Assignee Title
WO2001047033A1 (fr) * 1999-12-20 2001-06-28 Nippon Sheet Glass Co., Ltd. Transducteur photoelectrique et substrat pour transducteur photoelectrique
WO2010134416A1 (fr) * 2009-05-22 2010-11-25 東洋紡績株式会社 Film polyester hautement adhésif à usage optique
WO2011070714A1 (fr) * 2009-12-11 2011-06-16 日本板硝子株式会社 Verre de revêtement pour convertisseur photoélectrique et procédé pour sa production
JP2014015543A (ja) * 2012-07-09 2014-01-30 Nissan Chem Ind Ltd 低屈折率コーティング組成物
JP2014032248A (ja) * 2012-08-01 2014-02-20 Nippon Sheet Glass Co Ltd 光電変換装置用カバーガラス
WO2014084093A1 (fr) * 2012-11-27 2014-06-05 共栄社化学株式会社 Composition pour revêtement dur et article moulé comportant une couche de revêtement dur

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20230113808A (ko) 2020-12-15 2023-08-01 샌트랄 글래스 컴퍼니 리미티드 광학 부재용의 도포액, 중합체, 경화막, 감광성 도포액,패턴 경화막, 광학 부재, 고체 촬상 소자, 표시 장치, 폴리실록산 화합물, 도포액에 이용하는 안정화제, 경화막의 제조 방법, 패턴 경화막의 제조 방법, 및 중합체의 제조 방법
KR102738418B1 (ko) * 2024-08-30 2024-12-04 (주)선우이앤씨 저반사를 구현한 bipv 태양광 모듈

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