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WO2018198935A1 - Glass article with low-reflective coating - Google Patents

Glass article with low-reflective coating Download PDF

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Publication number
WO2018198935A1
WO2018198935A1 PCT/JP2018/016160 JP2018016160W WO2018198935A1 WO 2018198935 A1 WO2018198935 A1 WO 2018198935A1 JP 2018016160 W JP2018016160 W JP 2018016160W WO 2018198935 A1 WO2018198935 A1 WO 2018198935A1
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WO
WIPO (PCT)
Prior art keywords
reflection coating
low
fine particles
glass article
low reflection
Prior art date
Application number
PCT/JP2018/016160
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French (fr)
Japanese (ja)
Inventor
武司 籔田
瑞穂 小用
Original Assignee
日本板硝子株式会社
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Publication date
Application filed by 日本板硝子株式会社 filed Critical 日本板硝子株式会社
Priority to JP2019514443A priority Critical patent/JP7153638B2/en
Publication of WO2018198935A1 publication Critical patent/WO2018198935A1/en

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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

Definitions

  • the present invention relates to a glass article with a low reflection coating.
  • 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 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 stacked, but the low reflection coating is stacked. It is formed on the main surface opposite to the main surface, 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 incident side of sunlight, 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 substrate by dipping, flow coating, spraying, or the like.
  • JP-A-2013-537873 Patent Document 1
  • JP-A-4-82145 Patent Document 2
  • International Publication No. 2006/030848 Patent Document 3
  • a porous thin film formed by fixing silica (SiO 2 ) fine particles or magnesium fluoride (MgF 2 ) fine particles with a binder has been proposed.
  • an object of the present invention is to provide a glass article with a low reflection coating provided with a low reflection coating with further improved optical characteristics.
  • the present invention is a glass article with a low reflection coating comprising a glass substrate and a low reflection coating formed on at least a part of the surface of the glass substrate,
  • the low reflection coating is composed of fine particles and a binder,
  • the fine particles include MgF 2 fine particles as a main component,
  • the binder contains an inorganic oxide as a main component,
  • a glass article with a low reflection coating is provided.
  • the present invention it is possible to provide a glass article with a low-reflection coating having further improved optical characteristics as compared with a conventional glass article with a low-reflection coating.
  • the glass article with a low reflection coating includes a glass substrate and a low reflection coating formed on at least a part of the surface of the glass substrate.
  • the low reflection coating consists of fine particles and a binder.
  • the fine particles contain MgF 2 fine particles as a main component.
  • the binder contains an inorganic oxide as a main component.
  • the fine particles in the low reflection coating contain MgF 2 fine particles as a main component as described above.
  • that the fine particles contain MgF 2 fine particles as a main component means that the content of the MgF 2 fine particles in the fine particles is 95% by mass or more.
  • Particulates preferably comprises a MgF 2 particles less than 98 wt%, may be composed of only MgF 2 particles.
  • the fine particles in the low reflection coating may further contain fine particles other than MgF 2 fine particles.
  • the fine particles other than the MgF 2 fine particles are not particularly limited, and various functional fine particles capable of realizing a function to be added to the low reflection coating can be used.
  • TiO 2 fine particles that can impart photocatalytic performance to the low reflection coating can be used.
  • ZnO fine particles that can impart an ultraviolet cut function to the low reflection coating can be used.
  • SnO 2 fine particles that can impart an antistatic function to the low reflection coating can be used.
  • the MgF 2 fine particles preferably have an average particle size of 10 to 30 nm. According to the MgF 2 fine particles having such an average particle diameter, a highly transparent coating can be formed.
  • the “average particle size” of the fine particles means a particle size (D50) corresponding to 50% of volume accumulation in the particle size distribution measured by the laser diffraction particle size distribution measurement method.
  • the binder in the low reflection coating contains an inorganic oxide as a main component.
  • the binder containing an inorganic oxide as a main component means that the content of the inorganic oxide in the binder is 80% by mass or more.
  • the binder preferably contains 90% by mass or more of an inorganic oxide, and may be composed of only an inorganic oxide.
  • the binder may further contain an organic component.
  • the binder may be amorphous or crystalline.
  • the inorganic oxide contained in the binder may be an oxide of at least one metal selected from the group consisting of Si, Al, Zr, Ti, Sn, and Fe.
  • the inorganic oxide may be made of Si oxide, Si oxide and Al oxide, or Al oxide.
  • the binder is made of an oxide of Si, a coating having a low reflectance and a high transmittance can be obtained.
  • the binder is made of an oxide of Al, a coating having a high refractive index but a low reflectance can be obtained.
  • the wear resistance of the coating is improved when the binder is composed of Si oxide and Al oxide.
  • the inorganic oxide contained in the binder is composed of Si oxide and Al oxide, the Si oxide content is converted to SiO 2 , and the Al oxide content is converted to Al 2 O 3 .
  • the mass ratio (SiO 2 : Al 2 O 3 ) between SiO 2 and Al 2 O 3 in the inorganic oxide contained in the binder is preferably 99.5: 0.5 to 97: 3, for example.
  • the mass ratio of fine particles to binder (fine particles: binder) in the low reflection coating can be, for example, 95: 5 to 35:65.
  • the glass substrate for example, a glass plate, a glass substrate with a transparent conductive film, and a glass plate with a Low-E (Low-Emissivity) film are used.
  • a glass plate for example, a glass plate, a glass substrate with a transparent conductive film, and a glass plate with a Low-E (Low-Emissivity) film are used.
  • the example which uses a glass plate as a glass base material is demonstrated.
  • the glass plate is not particularly limited, but in order to smooth the surface of the low reflection coating provided on the main surface, a glass plate having excellent microscopic surface smoothness is preferable.
  • 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 in the present specification is a value defined in JIS B0601-1994.
  • the glass plate may be a template glass having macroscopic irregularities of a size that can be confirmed with the naked eye.
  • the macroscopic unevenness means unevenness having an average interval Sm of about millimeter order, which is confirmed when the evaluation length in the roughness curve is set to centimeter order.
  • the average spacing Sm of the irregularities on the surface of the template glass is preferably 0.3 mm or more, more preferably 0.4 mm or more, particularly preferably 0.45 mm or more, 2.5 mm or less, further 2.1 mm or less, particularly 2.0 mm or less. In particular, it is 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 specified in JIS (Japanese Industrial Standards) B0601-1994.
  • the arithmetic average roughness Ra can satisfy several nm or less, for example, 1 nm or less. Therefore, even a template glass can be suitably used as a glass substrate of the glass article with a low reflection coating of the present embodiment as a glass plate having excellent microscopic surface smoothness.
  • 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 glass plate may be a glass plate in which another coating is applied to the main surface opposite to the main surface on which the low reflection coating is formed.
  • a glass plate with a transparent conductive film is mentioned as a glass plate that can be suitably applied with the low reflection coating of the present embodiment.
  • This glass plate with a transparent conductive film has a transparent conductive film on one main surface of any of the glass plates described above, for example.
  • the transparent conductive film for example, one or more underlayers and a transparent conductive layer containing, for example, fluorine-doped tin oxide as a main component are sequentially laminated on the main surface of a glass plate.
  • the reflectance at the wavelength at which the reflectance is lowest (hereinafter referred to as the minimum reflectance) may be described with respect to the reflectance of the surface on which the low reflection coating is formed. ) Can be 2% or less, preferably 1.8% or less.
  • the glass article with a low reflection coating of the present embodiment has an average reflectance of the surface on which the low reflection coating is formed, with respect to the average reflectance in the wavelength range of 380 to 850 nm of the surface on which the low reflection coating is formed.
  • the difference obtained by subtracting the average reflectance of the surface in the state where the low-reflective coating is formed (hereinafter sometimes referred to as a reflectance reduction effect) from 3% or more, preferably 3.2% or more. It can be.
  • the glass article with a low reflection coating according to the present embodiment can have excellent reflection characteristics as described above.
  • the glass article with a low reflection coating of the present embodiment has an average transmittance of the surface on which the low reflection coating is formed with respect to the average transmittance in the wavelength range of 380 to 850 nm of the surface on which the low reflection coating is formed.
  • the difference obtained by subtracting the average transmittance of the surface in a state where the low-reflective coating is not formed (hereinafter also referred to as transmittance gain) from 2.9% or more, preferably 3.0% or more. can do.
  • the glass article with a low reflection coating of the present embodiment can have such excellent transmission characteristics.
  • the glass article with a low reflection coating of the present embodiment also has excellent wear resistance.
  • the glass article with a low reflection coating according to the present embodiment has a visible light reflectance before the test based on the visible light reflectance after the Taber abrasion test.
  • the difference obtained by subtracting the reflectance can be 3% or less, preferably 2.7% or less. The details of the Taber abrasion test will be described in Examples described later.
  • the glass article with a low reflection coating of the present embodiment can be formed by applying a coating liquid on the surface of a glass substrate such as a glass plate to form a coating film, and drying and curing the coating film.
  • a coating liquid on the surface of a glass substrate such as a glass plate to form a coating film
  • Any known method such as spin coating, roll coating, bar coating, dip coating, spray coating or the like can be used as a method for applying the coating liquid to the surface of the glass substrate.
  • Spray coating is excellent in terms of mass productivity.
  • Roll coating and bar coating are excellent in terms of homogeneity of the appearance of the coating film in addition to mass productivity.
  • the coating liquid contains fine particles contained in the low-reflective coating in the present embodiment and a substance that serves as a supply source of a compound such as an inorganic oxide constituting the binder.
  • a hydrolyzable silicon compound typified by silicon alkoxide can be used as a supply source of the oxide of Si.
  • 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. Hydrolysis of the hydrolyzable silicon compound can be performed as appropriate, and may be performed in a solution in which fine particles are present, or may be performed before mixing with the fine particles.
  • an acid and a base can be used for a hydrolysis catalyst
  • inorganic acids such as an acid, especially hydrochloric acid, nitric acid, a sulfuric acid, and phosphoric acid
  • hydrochloric acid it is more preferable to use hydrochloric acid. This is because the acidic solution is superior to the basic solution in terms of stability.
  • an aluminum halide can be used as a supply source of the Al oxide.
  • a preferred aluminum halide is aluminum chloride.
  • a disubstituted organotin compound such as dibutyltin dilaurate can be used as the Sn oxide supply source.
  • stannic chloride SnCl 4 .5H 2 O
  • SnO 2 can be obtained by dissolving stannic chloride (SnCl 4 .5H 2 O) in pure water and bringing the pH close to neutral with aqueous ammonia.
  • a glass plate with a transparent conductive film is used as a glass substrate of a glass article with a low reflection coating, and the low reflection on the surface of the glass plate on which the transparent conductive film is not provided. A coating was formed.
  • the transparent conductive film on the glass plate was removed by sandblasting, and a black paint was applied to the surface.
  • the reflectance curve was obtained by the same method for the reflectance of the glass plate before the low-reflection coating was formed.
  • the reflectance in the wavelength range of 380 to 850 nm was averaged to obtain the average reflectance before and after the formation of the low-reflection coating.
  • a difference obtained by subtracting the average reflectance after the formation of the low-reflection coating from the average reflectance before the formation of the low-reflection coating was determined to evaluate the effect of reducing the reflectance.
  • the transmittance curve transmission spectrum of the glass substrate (here, a glass plate) 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 glass plate on which the low-reflection coating was formed relative to the average transmittance of the glass plate before the low-reflection coating was formed was defined as a transmittance gain.
  • the low reflection coating was observed with a field emission scanning electron microscope (S-4500, manufactured by Hitachi, Ltd.). Further, from the FE-SEM photograph in the cross section from the upper side of the coating at an angle of 30 °, the average value of the coating thickness at five measurement points was defined as the film thickness of the low reflection coating.
  • Example 1 Preparation of coating solution> Tetraethoxysilane (normal ethyl silicate, manufactured by Tama Chemical Co., Ltd.) 34.7 g, 1-methoxy-2-propanol (solvent) 41.3 g, 1N hydrochloric acid (hydrolysis catalyst) 0.3 g, purified water 23.8 g And a hydrolysis reaction was carried out at 40 ° C. for 8 hours to obtain a hydrolysis liquid A having a solid content concentration of 10% by mass in terms of SiO 2 .
  • Tetraethoxysilane normal ethyl silicate, manufactured by Tama Chemical Co., Ltd.
  • 1-methoxy-2-propanol (solvent) 41.3 g
  • 1N hydrochloric acid (hydrolysis catalyst) 0.3 g
  • a hydrolysis reaction was carried out at 40 ° C. for 8 hours to obtain a hydrolysis liquid A having a solid content concentration of 10% by mass in terms of SiO 2 .
  • Example 1 0.6 g of hydrolyzed liquid A, 7 g of 1-methoxy-2-propanol (solvent), and 2.4 g of MgF 2 fine particle dispersion (manufactured by Stella Chemifa Co., Ltd., average particle size 20 nm, solid content concentration 10% by mass) are mixed with stirring.
  • the coating liquid of Example 1 was obtained.
  • the mass ratio of the solid content between the MgF 2 fine particles and the binder was 80.0: 20.0.
  • Example 1 a low reflection coating was formed on the main surface on one side of a glass plate with a transparent conductive film to obtain a glass article with a low reflection coating.
  • This glass plate is made of Nippon Soda Glass Co., Ltd., having a thickness of 3.2 mm, having a normal soda lime silicate composition, and having a transparent conductive layer including a transparent conductive layer formed on one main surface using an on-line CVD method. It was a glass plate with a transparent conductive film (TCO substrate).
  • This glass plate is cut into 200 ⁇ 300 mm, immersed in an alkaline solution (alkaline cleaning solution LBC-1, manufactured by Reybold Co., Ltd.), cleaned with an ultrasonic cleaner, washed with deionized water, and dried at room temperature. And a glass plate for forming a low reflection coating.
  • alkaline cleaning solution LBC-1 alkaline cleaning solution manufactured by Reybold Co., Ltd.
  • Example 1 the coating liquid of Example 1 was applied to the main surface of the glass plate on the side where the transparent conductive film was not applied by using a spin coating method. Specifically, the glass plate is held horizontally on a spin coater, a coating solution is dropped onto the center of the glass plate, the glass plate is rotated at a rotation speed of 1000 rpm, and the rotation speed is maintained for 10 seconds. The rotation of the glass plate was stopped. Thereby, the coating film for low reflection coating was formed on one main surface of the glass plate.
  • the coating film for low reflection coating was dried and cured with hot air.
  • This hot air drying uses a belt-conveying hot air drying device, the hot air set temperature is set to 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 performed by reciprocating four times and passing under the nozzle four times.
  • the glass plate on which the coating film for low reflection coating is formed is in contact with hot air for 140 seconds, and the maximum temperature reached on the glass surface on which the coating film for low reflection coating on the glass plate is formed is It was 200 ° C.
  • the glass plate after drying and curing was allowed to cool to room temperature, and a low reflection coating was formed on the glass plate.
  • the resulting low reflection coating thickness was 150 nm.
  • the obtained low reflection coating was held in an electric furnace set at 760 ° C., and the low reflection coating was subjected to heat treatment until the surface of the low reflection coating reached 500 ° C. Then, the glass plate with a low reflection coating was cooled to room temperature.
  • Example 2 ⁇ Preparation of coating solution> The amount of the hydrolyzed liquid A, 1-methoxy-2-propanol (solvent) and MgF 2 fine particle dispersion was changed to 1.2 g of hydrolyzed liquid A, 7 g of 1-methoxy-2-propanol (solvent), MgF 2 fine particle dispersion 1 A coating solution was prepared in the same manner as in Example 1 except that the amount was 0.8 g. In the coating liquid of Example 2, the solid content mass ratio (MgF 2 fine particles: binder) between the MgF 2 fine particles and the binder was 60.0: 40.0.
  • Example 2 a low reflection coating was formed on a glass plate in the same procedure as in Example 1 except that the coating liquid of Example 2 was used. However, unlike Example 1, the heat treatment for the formed low-reflection coating was not performed. The maximum temperature reached on the glass surface on which the coating film for low reflection coating on the glass plate was formed during hot air drying was 200 ° C. The resulting low reflection coating thickness was 165 nm. Moreover, each above-mentioned characteristic was evaluated about the obtained glass article with a low reflection coating. The results are shown in Table 1.
  • Example 3 ⁇ Preparation of coating solution> The amount of hydrolysis liquid A, 1-methoxy-2-propanol (solvent) and MgF 2 fine particle dispersion was 0.75 g of hydrolysis liquid A, 6.93 g of 1-methoxy-2-propanol (solvent), MgF 2 fine particle dispersion. Coating was conducted in the same manner as in Example 1 except that 0.025 g of Al 2 O 3 source (5% by mass aqueous solution of aluminum chloride hexahydrate (manufactured by Sigma-Aldrich), reagent grade) was added. A liquid was prepared. In the coating liquid of Example 3, the solid content mass ratio (MgF 2 fine particles: binder) between the MgF 2 fine particles and the binder was 73.5: 26.5.
  • Example 3 a low reflection coating was formed on a glass plate in the same procedure as in Example 1 except that the coating liquid of Example 3 was used. However, unlike Example 1, the heat treatment for the formed low-reflection coating was not performed. The maximum temperature reached on the glass surface on which the coating film for low reflection coating on the glass plate was formed during hot air drying was 200 ° C. The resulting low reflection coating thickness was 140 nm. About the obtained glass article with a low reflection coating, each above-mentioned characteristic was evaluated. The results are shown in Table 1. Further, FIG. 1 shows the result of observing the cross section of the glass article with a low reflection coating using an FE-SEM.
  • Example 4 Preparation of coating solution> The amount of hydrolysis liquid A, 1-methoxy-2-propanol (solvent) and MgF 2 fine particle dispersion was 0.90 g of hydrolysis liquid A, 6.96 g of 1-methoxy-2-propanol (solvent), MgF 2 fine particle dispersion. Coating was carried out in the same manner as in Example 1 except that 0.04 g of Al 2 O 3 source (aluminum chloride hexahydrate (Sigma Aldrich, reagent grade) 5 mass% aqueous solution) was added. A liquid was prepared. In the coating liquid of Example 4, the solid content mass ratio (MgF 2 fine particles: binder) between the MgF 2 fine particles and the binder was 69.3: 30.7.
  • Al 2 O 3 source aluminum chloride hexahydrate (Sigma Aldrich, reagent grade) 5 mass% aqueous solution
  • Example 4 a low reflection coating was formed on a glass plate in the same procedure as in Example 1 except that the coating liquid of Example 4 was used. However, unlike Example 1, the heat treatment for the formed low-reflection coating was not performed. The maximum temperature reached on the glass surface on which the coating film for low reflection coating on the glass plate was formed during hot air drying was 200 ° C. The resulting low reflection coating thickness was 150 nm. About the obtained glass article with a low reflection coating, each above-mentioned characteristic was evaluated. The results are shown in Table 1.
  • Example 5 ⁇ Preparation of coating solution> Aluminum chloride hexahydrate (manufactured by Sigma-Aldrich, reagent grade) 23.7 g, ethanol (solvent) 57.2 g, and purified water 19.1 g were mixed with stirring, followed by hydrolysis at 40 ° C. for 8 hours. A hydrolyzate B having a solid content concentration of 5% by mass in terms of 2 O 3 was obtained.
  • Example 1 except that hydrolyzate B was used in place of hydrolyzate A to obtain 1.05 g of hydrolyzate B, 7 g of 1-methoxy-2-propanol (solvent), and 1.9 g of MgF 2 fine particle dispersion.
  • a coating solution was prepared in the same manner as described above.
  • the solid content mass ratio (MgF 2 fine particles: binder) between the MgF 2 fine particles and the binder was 82.5: 17.5.
  • Example 5 a low reflection coating was applied to the glass plate in the same procedure as in Example 1 except that the coating liquid of Example 5 was used. In addition, the heat processing with respect to the formed low reflection coating was also performed similarly to Example 1. The maximum temperature reached on the glass surface on which the coating film for low reflection coating on the glass plate was formed during hot air drying was 200 ° C. The resulting low reflection coating thickness was 160 nm. About the obtained glass article with a low reflection coating, each above-mentioned characteristic was evaluated. The results are shown in Table 1.
  • Example 6 Preparation of coating solution> A coating solution was prepared in the same manner as in Example 1 except that the hydrolysis solution B prepared in Example 5 was used instead of the hydrolysis solution A. In the coating liquid of Example 6, the solid mass ratio (MgF 2 fine particles: binder) between the MgF 2 fine particles and the binder was 90.0: 10.0.
  • Example 6 a low reflection coating was applied to the glass plate in the same procedure as in Example 1 except that the coating liquid of Example 6 was used. In addition, the heat processing with respect to the formed low reflection coating was also performed similarly to Example 1. The maximum temperature reached on the glass surface on which the coating film for low reflection coating on the glass plate was formed during hot air drying was 200 ° C. The resulting low reflection coating thickness was 150 nm. About the obtained glass article with a low reflection coating, each above-mentioned characteristic was evaluated. The results are shown in Table 1.
  • Example 7 ⁇ Preparation of coating solution> The amount of hydrolyzed liquid A, 1-methoxy-2-propanol (solvent) and MgF 2 fine particle dispersion was 0.60 g of hydrolyzed liquid A, 7.37 g of 1-methoxy-2-propanol (solvent), MgF 2 fine particle dispersed Except that 0.2 g of TiO 2 fine particle dispersion (“STS-01”, manufactured by Ishihara Sangyo Co., Ltd., average particle size 10-30 nm, anatase type, X-ray particle size 7 nm) was added. Prepared a coating solution in the same manner as in Example 1.
  • STS-01 TiO 2 fine particle dispersion
  • the solid content mass ratio of the fine particles (total of MgF 2 fine particles and TiO 2 fine particles) to the binder (MgF 2 fine particles + TiO 2 fine particles: binder) was 79.2: 20.8. It was.
  • Example 7 a low reflection coating was applied to the glass plate in the same procedure as in Example 1 except that the coating liquid of Example 7 was used. In addition, the heat processing with respect to the formed low reflection coating was also performed similarly to Example 1. The maximum temperature reached on the glass surface on which the coating film for low reflection coating on the glass plate was formed during hot air drying was 200 ° C. The resulting low reflection coating thickness was 170 nm. About the obtained glass article with a low reflection coating, each above-mentioned characteristic was evaluated. The results are shown in Table 1.
  • the glass articles with low reflection coating of Examples 1 to 7 have a minimum reflectance as low as 2% or less, a difference in reflectance before and after formation of the low reflection coating (reflectance reduction effect) as high as 3% or more, and a transmittance gain. was as high as 2.9% or more and had excellent optical characteristics. Further, in the glass articles with low reflection coating of Examples 1 to 7, the decrease in visible light reflectance after the abrasion test was suppressed to 3% or less, and sufficient abrasion resistance was provided. Further, the glass article with a low reflection coating of Example 7 in which the low reflection coating contains TiO 2 fine particles had a contact angle of 5 degrees or less after UV irradiation, and a photocatalytic effect was also confirmed.
  • a glass article with a low reflection coating having excellent optical properties can be provided.

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Abstract

This glass article with low-reflective coating comprises: a glass substrate; and a low-reflective coating formed on at least a portion of the surface of the glass substrate. The low-reflective coating comprises fine particles and a binder. The fine particles contain MgF2 fine particles as a main component. The binder contains an inorganic oxide as a main component.

Description

低反射コーティング付きガラス物品Glass article with low reflection coating
　本発明は、低反射コーティング付きガラス物品に関する。 The present invention relates to a glass article with a low reflection coating.
　ガラス、セラミックなどの基材の表面には、その基材の用途における機能改善を目的として、光をより多く透過させるため、又は反射による眩惑を防止するために、低反射コーティングが形成される。 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.
　低反射コーティングは、車両用ガラス、ショーウィンドウ又は光電変換装置に用いるガラス板などに利用される。光電変換装置の一種であるいわゆる薄膜型太陽電池では、下地膜、透明導電膜、アモルファスシリコンなどからなる光電変換層及び裏面薄膜電極を順次積層したガラス板を用いるが、低反射コーティングはこれら積層した主表面とは対向する主表面、つまり太陽光が入射する側の主表面に形成される。このように太陽光の入射側に低反射コーティングが形成された太陽電池では、より多くの太陽光が光電変換層又は太陽電池素子に導かれ、その発電量が向上することになる。 低 Low reflection coating is used for glass for vehicle, show window or glass plate used for photoelectric conversion device. A so-called thin film 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 stacked, but the low reflection coating is stacked. It is formed on the main surface opposite to the main surface, 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 incident side of sunlight, more sunlight is guided to the photoelectric conversion layer or the solar cell element, and the power generation amount is improved.
　最もよく用いられる低反射コーティングは、真空蒸着法、スパッタリング法、化学蒸着法（ＣＶＤ法）などによる誘電体膜であるが、シリカ微粒子などの微粒子を含む微粒子含有膜が低反射コーティングとして用いられることもある。微粒子含有膜は、微粒子を含むコーティング液を、ディッピング法、フローコート法、スプレー法などによって基材上に塗布することにより成膜される。 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. There is also. The fine particle-containing film is formed by applying a coating liquid containing fine particles on a substrate by dipping, flow coating, spraying, or the like.
　例えば特表２０１３－５３７８７３号公報（特許文献１）、特開平４－８２１４５号公報（特許文献２）及び国際公開第２００６／０３０８４８号（特許文献３）には、ガラス板などの基材の表面に形成される低反射コーティングとして、シリカ（ＳｉＯ2）微粒子やフッ化マグネシウム（ＭｇＦ2）微粒子がバインダで固定されることによって形成されている多孔質薄膜が提案されている。 For example, JP-A-2013-537873 (Patent Document 1), JP-A-4-82145 (Patent Document 2) and International Publication No. 2006/030848 (Patent Document 3) describe the surface of a substrate such as a glass plate. As a low-reflective coating, a porous thin film formed by fixing silica (SiO 2 ) fine particles or magnesium fluoride (MgF 2 ) fine particles with a binder has been proposed.
特表２０１３－５３７８７３号公報JP 2013-537873 A 特開平４－８２１４５号公報JP-A-4-82145 国際公開第２００６／０３０８４８号International Publication No. 2006/030848
　従来の低反射コーティングについて、光学特性の向上、特に反射率の低減及び透過率の増大という点において、さらなる改善が求められていた。 For the conventional low-reflection coating, further improvement has been demanded in terms of improving optical characteristics, particularly in terms of reducing reflectance and increasing transmittance.
　本発明は、かかる事情に鑑み、光学特性がさらに向上した低反射コーティングを備えた低反射コーティング付きガラス物品を提供することを目的とする。 In view of such circumstances, an object of the present invention is to provide a glass article with a low reflection coating provided with a low reflection coating with further improved optical characteristics.
　本発明は、ガラス基材と、前記ガラス基材の表面の少なくとも一部に形成されている低反射コーティングとを含む低反射コーティング付きガラス物品であって、
　前記低反射コーティングは、微粒子とバインダとからなり、
　前記微粒子は、主成分としてＭｇＦ2微粒子を含み、
　前記バインダは、主成分として無機酸化物を含む、
低反射コーティング付きガラス物品を提供する。 The present invention is a glass article with a low reflection coating comprising a glass substrate and a low reflection coating formed on at least a part of the surface of the glass substrate,
The low reflection coating is composed of fine particles and a binder,
The fine particles include MgF 2 fine particles as a main component,
The binder contains an inorganic oxide as a main component,
A glass article with a low reflection coating is provided.
　本発明によれば、従来の低反射コーティング付きガラス物品と比較して光学特性がさらに向上した低反射コーティング付きガラス物品を提供できる。 According to the present invention, it is possible to provide a glass article with a low-reflection coating having further improved optical characteristics as compared with a conventional glass article with a low-reflection coating.
実施例３で得た低反射コーティング付きガラス物品を電界放射型走査型電子顕微鏡（ＦＥ－ＳＥＭ）で観察した結果を示す図である。It is a figure which shows the result of having observed the glass article with a low reflection coating obtained in Example 3 with the field emission scanning electron microscope (FE-SEM).
　本発明の低反射コーティング付きガラス物品の一実施形態について説明する。 An embodiment of a glass article with a low reflection coating according to the present invention will be described.
　本実施形態の低反射コーティング付きガラス物品は、ガラス基材と、そのガラス基材の表面の少なくとも一部に形成されている低反射コーティングとを含んでいる。低反射コーティングは、微粒子とバインダとからなる。微粒子は、主成分としてＭｇＦ2微粒子を含んでいる。バインダは、主成分として無機酸化物を含んでいる。以下に、本実施形態の低反射コーティング付きガラス物品について、より詳しく説明する。 The glass article with a low reflection coating according to the present embodiment includes a glass substrate and a low reflection coating formed on at least a part of the surface of the glass substrate. The low reflection coating consists of fine particles and a binder. The fine particles contain MgF 2 fine particles as a main component. The binder contains an inorganic oxide as a main component. Below, the glass article with a low reflection coating of this embodiment is demonstrated in detail.
　まず、低反射コーティングについて説明する。 First, the low reflection coating will be described.
　低反射コーティングにおける微粒子は、上述のとおり、主成分としてＭｇＦ2微粒子を含んでいる。ここで、微粒子が主成分としてＭｇＦ2微粒子を含むとは、微粒子におけるＭｇＦ2微粒子の含有率が９５質量％以上であることをいう。微粒子は、ＭｇＦ2微粒子を９８質量％以上含むことが好ましく、ＭｇＦ2微粒子のみから構成されていてもよい。 The fine particles in the low reflection coating contain MgF 2 fine particles as a main component as described above. Here, that the fine particles contain MgF 2 fine particles as a main component means that the content of the MgF 2 fine particles in the fine particles is 95% by mass or more. Particulates preferably comprises a MgF 2 particles less than 98 wt%, may be composed of only MgF 2 particles.
　低反射コーティングにおける微粒子は、ＭｇＦ2微粒子以外の微粒子をさらに含んでいてもよい。ＭｇＦ2微粒子以外の微粒子は、特には限定されず、低反射コーティングに追加したい機能を実現できる種々の機能性微粒子を用いることができる。例えば、光触媒性能を備えた低反射コーティングを実現する場合は、低反射コーティングに光触媒性能を付与し得るＴｉＯ2微粒子などを用いることができる。紫外線カット機能を備えた低反射コーティングを実現する場合は、低反射コーティングに紫外線カット機能を付与し得るＺｎＯ微粒子などを用いることができる。帯電防止機能を備えた低反射コーティングを実現する場合は、低反射コーティングに帯電防止機能を付与し得るＳｎＯ2微粒子などを用いることができる。 The fine particles in the low reflection coating may further contain fine particles other than MgF 2 fine particles. The fine particles other than the MgF 2 fine particles are not particularly limited, and various functional fine particles capable of realizing a function to be added to the low reflection coating can be used. For example, when realizing a low reflection coating having photocatalytic performance, TiO 2 fine particles that can impart photocatalytic performance to the low reflection coating can be used. In the case of realizing a low reflection coating having an ultraviolet cut function, ZnO fine particles that can impart an ultraviolet cut function to the low reflection coating can be used. When realizing a low reflection coating having an antistatic function, SnO 2 fine particles that can impart an antistatic function to the low reflection coating can be used.
　ＭｇＦ2微粒子は、平均粒径が１０～３０ｎｍであることが好ましい。このような平均粒径を有するＭｇＦ2微粒子によれば、透明性の高いコーティングを形成することが可能となる。ここで、微粒子の「平均粒径」とは、レーザー回折式粒度分布測定法により測定した粒度分布において、体積累積が５０％に相当する粒径（Ｄ５０）を意味する。 The MgF 2 fine particles preferably have an average particle size of 10 to 30 nm. According to the MgF 2 fine particles having such an average particle diameter, a highly transparent coating can be formed. Here, the “average particle size” of the fine particles means a particle size (D50) corresponding to 50% of volume accumulation in the particle size distribution measured by the laser diffraction particle size distribution measurement method.
　低反射コーティングにおけるバインダは、上述のとおり、主成分として無機酸化物を含む。ここで、バインダが主成分として無機酸化物を含むとは、バインダにおける無機酸化物の含有率が８０質量％以上であることをいう。バインダは、無機酸化物を９０質量％以上含むことが好ましく、無機酸化物のみから構成されていてもよい。バインダは、有機成分をさらに含んでいてもよい。バインダは、非晶質であってもよいし、結晶質であってもよい。 As described above, the binder in the low reflection coating contains an inorganic oxide as a main component. Here, the binder containing an inorganic oxide as a main component means that the content of the inorganic oxide in the binder is 80% by mass or more. The binder preferably contains 90% by mass or more of an inorganic oxide, and may be composed of only an inorganic oxide. The binder may further contain an organic component. The binder may be amorphous or crystalline.
　バインダに含まれる無機酸化物は、Ｓｉ、Ａｌ、Ｚｒ、Ｔｉ、Ｓｎ及びＦｅからなる群から選ばれる少なくともいずれか１種の金属の酸化物であってよい。例えば、無機酸化物がＳｉの酸化物からなっていてもよいし、Ｓｉの酸化物とＡｌの酸化物とからなっていてもよいし、Ａｌの酸化物からなっていてもよい。バインダがＳｉの酸化物からなることにより、低反射率及び高透過率のコーティングが得られる。バインダがＡｌの酸化物からなることにより、高屈折率バインダであるが低反射率のコーティングが得られる。バインダがＳｉの酸化物とＡｌの酸化物とからなることにより、コーティングの耐摩耗性が向上する。 The inorganic oxide contained in the binder may be an oxide of at least one metal selected from the group consisting of Si, Al, Zr, Ti, Sn, and Fe. For example, the inorganic oxide may be made of Si oxide, Si oxide and Al oxide, or Al oxide. When the binder is made of an oxide of Si, a coating having a low reflectance and a high transmittance can be obtained. When the binder is made of an oxide of Al, a coating having a high refractive index but a low reflectance can be obtained. The wear resistance of the coating is improved when the binder is composed of Si oxide and Al oxide.
　バインダに含まれる無機酸化物がＳｉの酸化物とＡｌの酸化物とからなり、Ｓｉの酸化物の含有量をＳｉＯ2に換算し、かつＡｌ酸化物の含有量をＡｌ2Ｏ3に換算した場合、バインダに含まれる無機酸化物におけるＳｉＯ2とＡｌ2Ｏ3との質量比（ＳｉＯ2：Ａｌ2Ｏ3）は、例えば９９．５：０．５～９７：３であることが好ましい。ＳｉＯ2とＡｌ2Ｏ3との質量比をこのような範囲とすることにより、透過率を向上させることができる。 The inorganic oxide contained in the binder is composed of Si oxide and Al oxide, the Si oxide content is converted to SiO 2 , and the Al oxide content is converted to Al 2 O 3 . In this case, the mass ratio (SiO 2 : Al 2 O 3 ) between SiO 2 and Al 2 O 3 in the inorganic oxide contained in the binder is preferably 99.5: 0.5 to 97: 3, for example. By setting the mass ratio of SiO 2 and Al 2 O 3 in such a range, the transmittance can be improved.
　低反射コーティングにおける微粒子とバインダとの質量比（微粒子：バインダ）は、例えば９５：５～３５：６５とできる。微粒子とバインダとの質量比をこのような範囲内とすることにより、高透過率を維持しつつ、実用に耐えうる耐久性を有するコーティングが得られる。 The mass ratio of fine particles to binder (fine particles: binder) in the low reflection coating can be, for example, 95: 5 to 35:65. By setting the mass ratio of the fine particles to the binder within such a range, a coating having durability that can withstand practical use can be obtained while maintaining high transmittance.
　次に、本実施形態の低反射コーティング付きガラス物品に用いられるガラス基材について説明する。 Next, the glass substrate used for the glass article with a low reflection coating according to this embodiment will be described.
　ガラス基材としては、例えば、ガラス板、透明導電膜付きガラス基板及びＬｏｗ－Ｅ（Low Emissivity）膜付きガラス板が用いられる。ここでは、ガラス基材としてガラス板を用いる例について説明する。 As the glass substrate, for example, a glass plate, a glass substrate with a transparent conductive film, and a glass plate with a Low-E (Low-Emissivity) film are used. Here, the example which uses a glass plate as a glass base material is demonstrated.
　ガラス板は、特に限定されないが、その主表面上に設けられる低反射コーティングの表面を平滑にするためには、微視的な表面の平滑性が優れているものが好ましい。たとえば、ガラス板は、その主表面の算術平均粗さＲａがたとえば１ｎｍ以下、好ましくは０．５ｎｍ以下の平滑性を有するフロート板ガラスであってもよい。ここで、本明細書における算術平均粗さＲａは、ＪＩＳ　Ｂ０６０１－１９９４に規定された値である。 The glass plate is not particularly limited, but in order to smooth the surface of the low reflection coating provided on the main surface, a glass plate having excellent microscopic surface smoothness is preferable. For example, 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. Here, the arithmetic average roughness Ra in the present specification is a value defined in JIS B0601-1994.
　一方で、ガラス板は、その表面に、肉眼で確認できるサイズの巨視的な凹凸を有する型板ガラスであってもよい。なお、ここでいう巨視的な凹凸とは、粗さ曲線における評価長さをセンチメートルオーダーとした際に確認される、平均間隔Ｓｍがミリメートルオーダー程度の凹凸のことである。型板ガラスの表面における凹凸の平均間隔Ｓｍは、０．３ｍｍ以上、さらに０．４ｍｍ以上、特に０．４５ｍｍ以上であることが好ましく、２．５ｍｍ以下、さらに２．１ｍｍ以下、特に２．０ｍｍ以下、とりわけ１．５ｍｍ以下であることが好ましい。ここで、平均間隔Ｓｍは、粗さ曲線が平均線と交差する点から求めた山谷一周期の間隔の平均値を意味する。さらに、型板ガラス板の表面凹凸は、上記範囲の平均間隔Ｓｍとともに、０．５μｍ～１０μｍ、特に１μｍ～８μｍの最大高さＲｙを有することが好ましい。ここで、平均間隔Ｓｍ及び最大高さＲｙは、ＪＩＳ（日本工業規格）　Ｂ０６０１－１９９４に規定された値である。なお、このような型板ガラスであっても、微視的には（例えば原子間力顕微鏡（ＡＦＭ）観察のような、粗さ曲線における評価長さが数１００ｎｍである表面粗さ測定では）、算術平均粗さＲａが数ｎｍ以下、例えば１ｎｍ以下を満たすことが可能である。したがって、型板ガラスであっても、微視的な表面の平滑性に優れるガラス板として、本実施形態の低反射コーティング付きガラス物品のガラス基材として好適に使用できる。 On the other hand, the glass plate may be a template glass having macroscopic irregularities of a size that can be confirmed with the naked eye. Here, the macroscopic unevenness means unevenness having an average interval Sm of about millimeter order, which is confirmed when the evaluation length in the roughness curve is set to centimeter order. The average spacing Sm of the irregularities on the surface of the template glass is preferably 0.3 mm or more, more preferably 0.4 mm or more, particularly preferably 0.45 mm or more, 2.5 mm or less, further 2.1 mm or less, particularly 2.0 mm or less. In particular, it is preferably 1.5 mm or less. Here, 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. Further, the surface irregularities of the template glass plate preferably have a maximum height Ry of 0.5 μm to 10 μm, particularly 1 μm to 8 μm, together with the average interval Sm in the above range. Here, the average interval Sm and the maximum height Ry are values specified in JIS (Japanese Industrial Standards) B0601-1994. Even with such a template glass, microscopically (for example, in the surface roughness measurement in which the evaluation length in the roughness curve is several hundreds of nanometers, such as observation with an atomic force microscope (AFM)), The arithmetic average roughness Ra can satisfy several nm or less, for example, 1 nm or less. Therefore, even a template glass can be suitably used as a glass substrate of the glass article with a low reflection coating of the present embodiment as a glass plate having excellent microscopic surface smoothness.
　なお、ガラス板は、通常の型板ガラスや建築用板ガラスと同様の組成であってよいが、着色成分を極力含まないことが好ましい。ガラス板において、代表的な着色成分である酸化鉄の含有率は、Ｆｅ2Ｏ3に換算して、０．０６質量％以下、特に０．０２質量％以下が好適である。 In addition, although 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. In the glass plate, 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 .
　また、ガラス板は、低反射コーティングが形成される主表面とは反対側の主表面に、別のコーティングが施されているガラス板であってもよい。例えば、本実施形態の低反射コーティングを好適に施すことができるガラス板として、透明導電膜付きガラス板が挙げられる。この透明導電膜付きガラス板は、例えば上述の何れかのガラス板の一方の主表面に透明導電膜を有するものである。透明導電膜は、例えば、ガラス板の主表面に、１層以上の下地層と、例えばフッ素ドープ酸化錫を主成分とする透明導電層とが順に積層されているものである。 Further, the glass plate may be a glass plate in which another coating is applied to the main surface opposite to the main surface on which the low reflection coating is formed. For example, a glass plate with a transparent conductive film is mentioned as a glass plate that can be suitably applied with the low reflection coating of the present embodiment. This glass plate with a transparent conductive film has a transparent conductive film on one main surface of any of the glass plates described above, for example. In the transparent conductive film, for example, one or more underlayers and a transparent conductive layer containing, for example, fluorine-doped tin oxide as a main component are sequentially laminated on the main surface of a glass plate.
　次に、本実施形態の低反射コーティング付きガラス物品の低反射コーティングの反射特性について説明する。 Next, the reflection characteristics of the low-reflection coating of the glass article with the low-reflection coating of this embodiment will be described.
　本実施形態の低反射コーティング付きガラス物品は、低反射コーティングが形成されている面の反射率について、当該反射率が最低となる波長における反射率（以下、最低反射率と記載することがある。）を２％以下、好ましくは１．８％以下とすることができる。 In the glass article with a low reflection coating of the present embodiment, the reflectance at the wavelength at which the reflectance is lowest (hereinafter referred to as the minimum reflectance) may be described with respect to the reflectance of the surface on which the low reflection coating is formed. ) Can be 2% or less, preferably 1.8% or less.
　また、本実施形態の低反射コーティング付きガラス物品は、低反射コーティングが形成されている面の波長域３８０～８５０ｎｍにおける平均反射率について、低反射コーティングが形成されていない状態の当該面の平均反射率から、低反射コーティングが形成されている状態の当該面の平均反射率を差し引いた差（以下、反射率低減効果と記載することがある。）を３％以上、好ましくは３．２％以上とすることができる。 In addition, the glass article with a low reflection coating of the present embodiment has an average reflectance of the surface on which the low reflection coating is formed, with respect to the average reflectance in the wavelength range of 380 to 850 nm of the surface on which the low reflection coating is formed. The difference obtained by subtracting the average reflectance of the surface in the state where the low-reflective coating is formed (hereinafter sometimes referred to as a reflectance reduction effect) from 3% or more, preferably 3.2% or more. It can be.
　本実施形態の低反射コーティング付きガラス物品は、以上のような優れた反射特性を有することができる。 The glass article with a low reflection coating according to the present embodiment can have excellent reflection characteristics as described above.
　また、本実施形態の低反射コーティング付きガラス物品は、低反射コーティングが形成されている面の波長域３８０～８５０ｎｍにおける平均透過率について、低反射コーティングが形成されている状態の当該面の平均透過率から、低反射コーティングが形成されていない状態の当該面の平均透過率を差し引いた差（以下、透過率ゲインということがある。）を２．９％以上、好ましくは３．０％以上とすることができる。本実施形態の低反射コーティング付きガラス物品は、このような優れた透過特性を有することができる。 In addition, the glass article with a low reflection coating of the present embodiment has an average transmittance of the surface on which the low reflection coating is formed with respect to the average transmittance in the wavelength range of 380 to 850 nm of the surface on which the low reflection coating is formed. The difference obtained by subtracting the average transmittance of the surface in a state where the low-reflective coating is not formed (hereinafter also referred to as transmittance gain) from 2.9% or more, preferably 3.0% or more. can do. The glass article with a low reflection coating of the present embodiment can have such excellent transmission characteristics.
　また、本実施形態の低反射コーティング付きガラス物品は、優れた耐摩耗性も有する。具体的には、本実施形態の低反射コーティング付きガラス物品は、低反射コーティングが形成されている面の可視光反射率について、テーバー摩耗試験後の可視光反射率から、前記試験前の可視光反射率を差し引いた差を３％以下、好ましくは２．７％以下とすることができる。なお、テーバー摩耗試験については、後述の実施例においてその詳細を説明する。 Moreover, the glass article with a low reflection coating of the present embodiment also has excellent wear resistance. Specifically, the glass article with a low reflection coating according to the present embodiment has a visible light reflectance before the test based on the visible light reflectance after the Taber abrasion test. The difference obtained by subtracting the reflectance can be 3% or less, preferably 2.7% or less. The details of the Taber abrasion test will be described in Examples described later.
　本実施形態の低反射コーティング付きガラス物品は、ガラス板などのガラス基材の表面にコーティング液を塗布して塗膜を形成し、その塗膜を乾燥及び硬化させることによって形成できる。コーティング液をガラス基材の表面に塗布する方法には、公知の任意の方法、例えばスピンコーティング、ロールコーティング、バーコーティング、ディップコーティング、スプレーコーティングなど、を用いることができる。スプレーコーティングは量産性の点で優れている。ロールコーティングやバーコーティングは量産性に加えて塗膜外観の均質性の点で優れている。 The glass article with a low reflection coating of the present embodiment can be formed by applying a coating liquid on the surface of a glass substrate such as a glass plate to form a coating film, and drying and curing the coating film. Any known method such as spin coating, roll coating, bar coating, dip coating, spray coating or the like can be used as a method for applying the coating liquid to the surface of the glass substrate. Spray coating is excellent in terms of mass productivity. Roll coating and bar coating are excellent in terms of homogeneity of the appearance of the coating film in addition to mass productivity.
　コーティング液には、本実施形態における低反射コーティングに含まれる微粒子と、バインダを構成する無機酸化物などの化合物の供給源となる物質とが含まれている。 The coating liquid contains fine particles contained in the low-reflective coating in the present embodiment and a substance that serves as a supply source of a compound such as an inorganic oxide constituting the binder.
　例えば、バインダがＳｉの酸化物を含む場合、Ｓｉの酸化物の供給源としては、例えばシリコンアルコキシドに代表される加水分解性シリコン化合物を用いることができる。シリコンアルコキシドとしては、テトラメトキシシラン、テトラエトキシシラン、テトライソプロポキシシランを例示できる。これら加水分解性シリコン化合物は、いわゆるゾルゲル法により加水分解及び縮重合してバインダとすればよい。加水分解性シリコン化合物の加水分解は、適宜実施することができ、微粒子が存在する溶液中で実施されてもよいし、微粒子と混合される前に実施されてもよい。なお、加水分解触媒には酸・塩基いずれを用いることもできるが、酸、特に塩酸、硝酸、硫酸及びリン酸などの無機酸を用いることが好しく、塩酸を用いることがさらに好ましい。塩基性より酸性の方が、コーティング液の安定性に優れるからである。 For example, when the binder contains an oxide of Si, for example, a hydrolyzable silicon compound typified by silicon alkoxide can be used as a supply source of the oxide of Si. Examples of 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. Hydrolysis of the hydrolyzable silicon compound can be performed as appropriate, and may be performed in a solution in which fine particles are present, or may be performed before mixing with the fine particles. In addition, although an acid and a base can be used for a hydrolysis catalyst, it is preferable to use inorganic acids, such as an acid, especially hydrochloric acid, nitric acid, a sulfuric acid, and phosphoric acid, and it is more preferable to use hydrochloric acid. This is because the acidic solution is superior to the basic solution in terms of stability.
　また、例えばバインダがＡｌの酸化物を含む場合、Ａｌの酸化物の供給源としては、例えばハロゲン化アルミニウムを用いることができる。好ましいハロゲン化アルミニウムは、塩化アルミニウムである。 For example, when the binder includes an oxide of Al, for example, an aluminum halide can be used as a supply source of the Al oxide. A preferred aluminum halide is aluminum chloride.
　また、例えばバインダがＳｎの酸化物を含む場合、Ｓｎの酸化物の供給源としては、例えばジブチルスズジラウレートなどの２置換の有機スズ化合物を用いることができる。また、塩化第二スズ（ＳｎＣｌ4・５Ｈ2Ｏ）も使用できる。例えば、塩化第二スズ（ＳｎＣｌ4・５Ｈ2Ｏ）を純水に溶かし、アンモニア水でｐＨを中性に近づけることで、ＳｎＯ2が得られる。 For example, when the binder includes Sn oxide, a disubstituted organotin compound such as dibutyltin dilaurate can be used as the Sn oxide supply source. Further, stannic chloride (SnCl 4 .5H 2 O) can also be used. For example, SnO 2 can be obtained by dissolving stannic chloride (SnCl 4 .5H 2 O) in pure water and bringing the pH close to neutral with aqueous ammonia.
　以下、実施例により、本発明をさらに詳細に説明する。まず、各実施例、各比較例において、ガラス基材（ここではガラス板）の表面上に形成した低反射コーティングの各特性の評価方法を説明する。 Hereinafter, the present invention will be described in more detail with reference to examples. First, in each example and each comparative example, an evaluation method for each characteristic of a low reflection coating formed on the surface of a glass substrate (here, a glass plate) will be described.
（反射特性）
　後述のとおり、本実施例及び比較例では、低反射コーティング付きガラス物品のガラス基材として透明導電膜付きガラス板が用いられ、ガラス板の透明導電膜が設けられていない側の面に低反射コーティングが形成された。反射率の測定では、低反射コーティングのみの反射率を測定するために、ガラス板の透明導電膜をサンドブラストにより除去し、その面に黒色塗料を塗布した。 (Reflection characteristics)
As will be described later, in this example and the comparative example, a glass plate with a transparent conductive film is used as a glass substrate of a glass article with a low reflection coating, and the low reflection on the surface of the glass plate on which the transparent conductive film is not provided. A coating was formed. In the measurement of the reflectance, in order to measure the reflectance of only the low-reflection coating, the transparent conductive film on the glass plate was removed by sandblasting, and a black paint was applied to the surface.
　分光光度計（「Ｕ－４１００」、株式会社日立ハイテクサイエンス製）を用い、積分球の窓に低反射コーティング付きのガラス板を接着して、ガラス板における低反射コーティングが形成された面の反射率曲線（反射スペクトル）を測定した。 Using a spectrophotometer ("U-4100", manufactured by Hitachi High-Tech Science Co., Ltd.), a glass plate with a low-reflection coating is adhered to the window of the integrating sphere, and the reflection of the surface of the glass plate on which the low-reflection coating is formed A rate curve (reflection spectrum) was measured.
　この反射率曲線から最低反射率を求めた。 The minimum reflectance was obtained from this reflectance curve.
　また、低反射コーティングが形成される前のガラス板の反射率についても、同様の方法で反射率曲線を求めた。低反射コーティング形成前後のガラス板の反射率について、波長域３８０～８５０ｎｍにおける反射率を平均化し、低反射コーティング形成前後の平均反射率を求めた。低反射コーティング形成前の前記平均反射率から、低反射コーティング形成後の平均反射率を差し引いた差を求めて、反射率低減効果の評価を行った。 Also, the reflectance curve was obtained by the same method for the reflectance of the glass plate before the low-reflection coating was formed. With respect to the reflectance of the glass plate before and after the formation of the low-reflection coating, the reflectance in the wavelength range of 380 to 850 nm was averaged to obtain the average reflectance before and after the formation of the low-reflection coating. A difference obtained by subtracting the average reflectance after the formation of the low-reflection coating from the average reflectance before the formation of the low-reflection coating was determined to evaluate the effect of reducing the reflectance.
（透過特性）
　分光光度計（ＵＶ－３１００ＰＣ、株式会社島津製作所製）を用い、低反射コーティングの形成前後におけるガラス基材（ここではガラス板）の透過率曲線（透過スペクトル）をそれぞれ測定した。平均透過率は、波長３８０～８５０ｎｍにおける透過率を平均化して算出した。低反射コーティングが形成されたガラス板の平均透過率の、該低反射コーティングが形成される前のガラス板の平均透過率に対する増分を透過率ゲインとした。 (Transmission characteristics)
Using a spectrophotometer (UV-3100PC, manufactured by Shimadzu Corporation), the transmittance curve (transmission spectrum) of the glass substrate (here, a glass plate) 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 glass plate on which the low-reflection coating was formed relative to the average transmittance of the glass plate before the low-reflection coating was formed was defined as a transmittance gain.
（ＳＥＭ観察）
　低反射コーティングを電界放射型走査型電子顕微鏡（Ｓ－４５００、株式会社日立製作所製）によって観察した。また、コーティングの３０°斜め上方からの断面におけるＦＥ－ＳＥＭ写真から、測定点５点でのコーティングの厚みの平均値を、低反射コーティングの膜厚とした。 (SEM observation)
The low reflection coating was observed with a field emission scanning electron microscope (S-4500, manufactured by Hitachi, Ltd.). Further, from the FE-SEM photograph in the cross section from the upper side of the coating at an angle of 30 °, the average value of the coating thickness at five measurement points was defined as the film thickness of the low reflection coating.
（耐摩耗性）
　テーバー摩耗試験として、テーバー往復摩耗試験機（Ｔａｂｅｒ社製）を用い、ガラス板の低反射コーティングが形成されている面を摩耗子ＣＳ－１０Ｆにて２５０回摩耗した。このテーバー摩耗試験後に、摩耗部の可視光反射率の変化を色差計（「ＣＭ２６００ｄ」、コニカミノルタ株式会社製）にて計測した。 (Abrasion resistance)
As a Taber abrasion test, a Taber reciprocating abrasion tester (manufactured by Taber) was used, and the surface of the glass plate on which the low-reflection coating was formed was worn 250 times with a wearer CS-10F. After this Taber abrasion test, the change in visible light reflectance of the worn part was measured with a color difference meter (“CM2600d”, manufactured by Konica Minolta, Inc.).
（光触媒効果）
　低反射コーティングが形成されたガラス板を、紫外線ランプ照射下（１ｍＷ／ｍ2）で４８時間放置した。その後に、水滴の表面接触角を計測して光触媒効果を評価した。 (Photocatalytic effect)
The glass plate on which the low-reflection coating was formed was left for 48 hours under ultraviolet lamp irradiation (1 mW / m 2 ). Thereafter, the surface contact angle of the water droplet was measured to evaluate the photocatalytic effect.
（実施例１）
＜コーティング液の調製＞
　テトラエトキシシランン（正珪酸エチル、多摩化学工業株式会社製）３４．７ｇ、１－メトキシ－２－プロパノール（溶媒）４１．３ｇ、１Ｎ塩酸（加水分解触媒）０．３ｇ、精製水２３．８ｇを攪拌混合し、４０℃にて８時間加水分解反応を行い、ＳｉＯ2換算での固形分濃度が１０質量％の加水分解液Ａを得た。 Example 1
<Preparation of coating solution>
Tetraethoxysilane (normal ethyl silicate, manufactured by Tama Chemical Co., Ltd.) 34.7 g, 1-methoxy-2-propanol (solvent) 41.3 g, 1N hydrochloric acid (hydrolysis catalyst) 0.3 g, purified water 23.8 g And a hydrolysis reaction was carried out at 40 ° C. for 8 hours to obtain a hydrolysis liquid A having a solid content concentration of 10% by mass in terms of SiO 2 .
　加水分解液Ａ０．６ｇ、１－メトキシ－２－プロパノール（溶媒）７ｇ、ＭｇＦ2微粒子分散液（ステラケミファ株式会社製、平均粒径２０ｎｍ、固形分濃度１０質量％）２．４ｇを攪拌混合し、実施例１のコーティング液を得た。実施例１のコーティング液において、ＭｇＦ2微粒子とバインダとの固形分質量比（ＭｇＦ2微粒子：バインダ）は、８０．０：２０．０であった。 0.6 g of hydrolyzed liquid A, 7 g of 1-methoxy-2-propanol (solvent), and 2.4 g of MgF 2 fine particle dispersion (manufactured by Stella Chemifa Co., Ltd., average particle size 20 nm, solid content concentration 10% by mass) are mixed with stirring. The coating liquid of Example 1 was obtained. In the coating liquid of Example 1, the mass ratio of the solid content between the MgF 2 fine particles and the binder (MgF 2 fine particles: binder) was 80.0: 20.0.
＜低反射コーティングの形成＞
　実施例１では、透明導電膜付きガラス板の片側の主表面に低反射コーティングを形成して、低反射コーティング付きガラス物品を得た。このガラス板は、通常のソーダライムシリケート組成からなり、オンラインＣＶＤ法を用いて片方の主表面に透明導電層を含む透明導電膜が形成された、厚さ３．２ｍｍの日本板硝子株式会社製の透明導電膜付きガラス板（ＴＣＯ基板）であった。このガラス板を２００×３００ｍｍに切断し、アルカリ溶液（アルカリ性洗浄液　ＬＢＣ－１、レイボルド株式会社製）に浸漬して超音波洗浄機を用いて洗浄し、脱イオン水で水洗したのち常温で乾燥させて低反射コーティングを形成するためのガラス板とした。低反射コーティングを施す前のこのガラス板の透過特性を前述のとおり評価したところ、平均透過率８０．０％であった。 <Formation of low-reflection coating>
In Example 1, a low reflection coating was formed on the main surface on one side of a glass plate with a transparent conductive film to obtain a glass article with a low reflection coating. This glass plate is made of Nippon Soda Glass Co., Ltd., having a thickness of 3.2 mm, having a normal soda lime silicate composition, and having a transparent conductive layer including a transparent conductive layer formed on one main surface using an on-line CVD method. It was a glass plate with a transparent conductive film (TCO substrate). This glass plate is cut into 200 × 300 mm, immersed in an alkaline solution (alkaline cleaning solution LBC-1, manufactured by Reybold Co., Ltd.), cleaned with an ultrasonic cleaner, washed with deionized water, and dried at room temperature. And a glass plate for forming a low reflection coating. When the transmission characteristics of this glass plate before applying the low reflection coating were evaluated as described above, the average transmittance was 80.0%.
　実施例１においては、スピンコート法を用い、前述のガラス板の透明導電膜が施されていない側の主表面に実施例１のコーティング液を塗布した。具体的には、ガラス板をスピンコート装置上で水平に保持し、ガラス板の中央部にコーティング液を滴下し、ガラス板を回転数１０００ｒｐｍで回転させ、１０秒間その回転数を保持した後、ガラス板の回転を停止させた。これにより、ガラス板の一方の主表面上に低反射コーティング用塗膜が形成された。 In Example 1, the coating liquid of Example 1 was applied to the main surface of the glass plate on the side where the transparent conductive film was not applied by using a spin coating method. Specifically, the glass plate is held horizontally on a spin coater, a coating solution is dropped onto the center of the glass plate, the glass plate is rotated at a rotation speed of 1000 rpm, and the rotation speed is maintained for 10 seconds. The rotation of the glass plate was stopped. Thereby, the coating film for low reflection coating was formed on one main surface of the glass plate.
　次いで、この低反射コーティング用塗膜を、熱風で乾燥・硬化させた。この熱風乾燥は、ベルト搬送式の熱風乾燥装置を用い、熱風の設定温度を３００℃、熱風吐出ノズルとガラス板との間の距離を５ｍｍ、搬送速度を０．５ｍ／分に設定し、２回往復してノズルの下を４回通過させることで行なった。このとき、低反射コーティング用塗膜が形成されているガラス板が熱風に触れている時間は１４０秒であり、ガラス板の低反射コーティング用塗膜が形成されているガラス面における最高到達温度は２００℃だった。乾燥・硬化後のガラス板は室温まで放冷し、ガラス板に低反射コーティングが形成された。得られた低反射コーティングの厚さは１５０ｎｍであった。得られた低反射コーティングを７６０℃に設定された電気炉内に保持し、低反射コーティングの表面が５００℃に達するまで、低反射コーティングに対し加熱処理を行った。その後、低反射コーティング付きガラス板を室温まで冷却した。 Next, the coating film for low reflection coating was dried and cured with hot air. This hot air drying uses a belt-conveying hot air drying device, the hot air set temperature is set to 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 performed by reciprocating four times and passing under the nozzle four times. At this time, the glass plate on which the coating film for low reflection coating is formed is in contact with hot air for 140 seconds, and the maximum temperature reached on the glass surface on which the coating film for low reflection coating on the glass plate is formed is It was 200 ° C. The glass plate after drying and curing was allowed to cool to room temperature, and a low reflection coating was formed on the glass plate. The resulting low reflection coating thickness was 150 nm. The obtained low reflection coating was held in an electric furnace set at 760 ° C., and the low reflection coating was subjected to heat treatment until the surface of the low reflection coating reached 500 ° C. Then, the glass plate with a low reflection coating was cooled to room temperature.
　こうして得た低反射コーティング付きガラス物品について、前述の各特性を評価した。その結果を表１に示す。 The above-mentioned characteristics of the glass article with a low reflection coating thus obtained were evaluated. The results are shown in Table 1.
（実施例２）
＜コーティング液の調製＞
　加水分解液Ａ、１－メトキシ－２－プロパノール（溶媒）及びＭｇＦ2微粒子分散液の量を、加水分解液Ａ１．２ｇ、１－メトキシ－２－プロパノール（溶媒）７ｇ、ＭｇＦ2微粒子分散液１．８ｇとした以外は、実施例１と同様にコーティング液を調製した。実施例２のコーティング液において、ＭｇＦ2微粒子とバインダとの固形分質量比（ＭｇＦ2微粒子：バインダ）は、６０．０：４０．０であった。 (Example 2)
<Preparation of coating solution>
The amount of the hydrolyzed liquid A, 1-methoxy-2-propanol (solvent) and MgF 2 fine particle dispersion was changed to 1.2 g of hydrolyzed liquid A, 7 g of 1-methoxy-2-propanol (solvent), MgF 2 fine particle dispersion 1 A coating solution was prepared in the same manner as in Example 1 except that the amount was 0.8 g. In the coating liquid of Example 2, the solid content mass ratio (MgF 2 fine particles: binder) between the MgF 2 fine particles and the binder was 60.0: 40.0.
＜低反射コーティングの形成＞
　実施例２では、前述の実施例２のコーティング液を用いた以外は、実施例１と同じ手順でガラス板に低反射コーティングを形成した。ただし、実施例１とは異なり、形成された低反射コーティングに対する加熱処理は行われなかった。熱風乾燥時の、ガラス板の低反射コーティング用塗膜が形成されているガラス面における最高到達温度は２００℃だった。得られた低反射コーティングの厚さは１６５ｎｍであった。また、得られた低反射コーティング付きガラス物品について、前述の各特性を評価した。その結果を表１に示す。 <Formation of low-reflection coating>
In Example 2, a low reflection coating was formed on a glass plate in the same procedure as in Example 1 except that the coating liquid of Example 2 was used. However, unlike Example 1, the heat treatment for the formed low-reflection coating was not performed. The maximum temperature reached on the glass surface on which the coating film for low reflection coating on the glass plate was formed during hot air drying was 200 ° C. The resulting low reflection coating thickness was 165 nm. Moreover, each above-mentioned characteristic was evaluated about the obtained glass article with a low reflection coating. The results are shown in Table 1.
（実施例３）
＜コーティング液の調製＞
　加水分解液Ａ、１－メトキシ－２－プロパノール（溶媒）及びＭｇＦ2微粒子分散液の量を、加水分解液Ａ０．７５ｇ、１－メトキシ－２－プロパノール（溶媒）６．９３ｇ、ＭｇＦ2微粒子分散液２．２５ｇとし、さらにＡｌ2Ｏ3源（塩化アルミニウム６水和物（シグマアルドリッチ社製、試薬グレード）の５質量％水溶液）を０．０７ｇ添加した以外は、実施例１と同様にコーティング液を調製した。実施例３のコーティング液において、ＭｇＦ2微粒子とバインダとの固形分質量比（ＭｇＦ2微粒子：バインダ）は、７３．５：２６．５であった。 (Example 3)
<Preparation of coating solution>
The amount of hydrolysis liquid A, 1-methoxy-2-propanol (solvent) and MgF 2 fine particle dispersion was 0.75 g of hydrolysis liquid A, 6.93 g of 1-methoxy-2-propanol (solvent), MgF 2 fine particle dispersion. Coating was conducted in the same manner as in Example 1 except that 0.025 g of Al 2 O 3 source (5% by mass aqueous solution of aluminum chloride hexahydrate (manufactured by Sigma-Aldrich), reagent grade) was added. A liquid was prepared. In the coating liquid of Example 3, the solid content mass ratio (MgF 2 fine particles: binder) between the MgF 2 fine particles and the binder was 73.5: 26.5.
＜低反射コーティングの形成＞
　実施例３では、前述の実施例３のコーティング液を用いた以外は、実施例１と同じ手順でガラス板に低反射コーティングを形成した。ただし、実施例１とは異なり、形成された低反射コーティングに対する加熱処理は行われなかった。熱風乾燥時の、ガラス板の低反射コーティング用塗膜が形成されているガラス面における最高到達温度は２００℃だった。得られた低反射コーティングの厚さは１４０ｎｍであった。得られた低反射コーティング付きガラス物品について、前述の各特性を評価した。その結果を表１に示す。また、低反射コーティング付きガラス物品の断面をＦＥ－ＳＥＭを用いて観察した結果を図１に示す。 <Formation of low-reflection coating>
In Example 3, a low reflection coating was formed on a glass plate in the same procedure as in Example 1 except that the coating liquid of Example 3 was used. However, unlike Example 1, the heat treatment for the formed low-reflection coating was not performed. The maximum temperature reached on the glass surface on which the coating film for low reflection coating on the glass plate was formed during hot air drying was 200 ° C. The resulting low reflection coating thickness was 140 nm. About the obtained glass article with a low reflection coating, each above-mentioned characteristic was evaluated. The results are shown in Table 1. Further, FIG. 1 shows the result of observing the cross section of the glass article with a low reflection coating using an FE-SEM.
（実施例４）
＜コーティング液の調製＞
　加水分解液Ａ、１－メトキシ－２－プロパノール（溶媒）及びＭｇＦ2微粒子分散液の量を、加水分解液Ａ０．９０ｇ、１－メトキシ－２－プロパノール（溶媒）６．９６ｇ、ＭｇＦ2微粒子分散液２．１０ｇとし、さらにＡｌ2Ｏ3源（塩化アルミニウム６水和物（シグマアルドリッチ社製、試薬グレード）の５質量％水溶液）を０．０４ｇ添加した以外は、実施例１と同様にコーティング液を調製した。実施例４のコーティング液において、ＭｇＦ2微粒子とバインダとの固形分質量比（ＭｇＦ2微粒子：バインダ）は、６９．３：３０．７であった。 Example 4
<Preparation of coating solution>
The amount of hydrolysis liquid A, 1-methoxy-2-propanol (solvent) and MgF 2 fine particle dispersion was 0.90 g of hydrolysis liquid A, 6.96 g of 1-methoxy-2-propanol (solvent), MgF 2 fine particle dispersion. Coating was carried out in the same manner as in Example 1 except that 0.04 g of Al 2 O 3 source (aluminum chloride hexahydrate (Sigma Aldrich, reagent grade) 5 mass% aqueous solution) was added. A liquid was prepared. In the coating liquid of Example 4, the solid content mass ratio (MgF 2 fine particles: binder) between the MgF 2 fine particles and the binder was 69.3: 30.7.
＜低反射コーティングの形成＞
　実施例４では、前述の実施例４のコーティング液を用いた以外は、実施例１と同じ手順でガラス板に低反射コーティングを形成した。ただし、実施例１とは異なり、形成された低反射コーティングに対する加熱処理は行われなかった。熱風乾燥時の、ガラス板の低反射コーティング用塗膜が形成されているガラス面における最高到達温度は２００℃だった。得られた低反射コーティングの厚さは１５０ｎｍであった。得られた低反射コーティング付きガラス物品について、前述の各特性を評価した。その結果を表１に示す。 <Formation of low-reflection coating>
In Example 4, a low reflection coating was formed on a glass plate in the same procedure as in Example 1 except that the coating liquid of Example 4 was used. However, unlike Example 1, the heat treatment for the formed low-reflection coating was not performed. The maximum temperature reached on the glass surface on which the coating film for low reflection coating on the glass plate was formed during hot air drying was 200 ° C. The resulting low reflection coating thickness was 150 nm. About the obtained glass article with a low reflection coating, each above-mentioned characteristic was evaluated. The results are shown in Table 1.
（実施例５）
＜コーティング液の調製＞
　塩化アルミニウム６水和物（シグマアルドリッチ社製、試薬グレード）２３．７ｇ、エタノール（溶媒）５７．２ｇ、精製水１９．１ｇを攪拌混合し、４０℃にて８時間加水分解反応を行い、Ａｌ2Ｏ3換算での固形分濃度５質量％の加水分解液Ｂを得た。 (Example 5)
<Preparation of coating solution>
Aluminum chloride hexahydrate (manufactured by Sigma-Aldrich, reagent grade) 23.7 g, ethanol (solvent) 57.2 g, and purified water 19.1 g were mixed with stirring, followed by hydrolysis at 40 ° C. for 8 hours. A hydrolyzate B having a solid content concentration of 5% by mass in terms of 2 O 3 was obtained.
　加水分解液Ａの代わりに加水分解液Ｂを用いて、加水分解液Ｂ１．０５ｇ、１－メトキシ－２－プロパノール（溶媒）７ｇ、ＭｇＦ2微粒子分散液１．９ｇとした以外は、実施例１と同様にコーティング液を調製した。実施例５のコーティング液において、ＭｇＦ2微粒子とバインダとの固形分質量比（ＭｇＦ2微粒子：バインダ）は、８２．５：１７．５であった。 Example 1 except that hydrolyzate B was used in place of hydrolyzate A to obtain 1.05 g of hydrolyzate B, 7 g of 1-methoxy-2-propanol (solvent), and 1.9 g of MgF 2 fine particle dispersion. A coating solution was prepared in the same manner as described above. In the coating liquid of Example 5, the solid content mass ratio (MgF 2 fine particles: binder) between the MgF 2 fine particles and the binder was 82.5: 17.5.
＜低反射コーティングの形成＞
　実施例５では、前述の実施例５のコーティング液を用いた以外は、実施例１と同じ手順でガラス板に低反射コーティングを施した。なお、形成された低反射コーティングに対する加熱処理も、実施例１と同様に行われた。熱風乾燥時の、ガラス板の低反射コーティング用塗膜が形成されているガラス面における最高到達温度は２００℃だった。得られた低反射コーティングの厚さは１６０ｎｍであった。得られた低反射コーティング付きガラス物品について、前述の各特性を評価した。その結果を表１に示す。 <Formation of low-reflection coating>
In Example 5, a low reflection coating was applied to the glass plate in the same procedure as in Example 1 except that the coating liquid of Example 5 was used. In addition, the heat processing with respect to the formed low reflection coating was also performed similarly to Example 1. The maximum temperature reached on the glass surface on which the coating film for low reflection coating on the glass plate was formed during hot air drying was 200 ° C. The resulting low reflection coating thickness was 160 nm. About the obtained glass article with a low reflection coating, each above-mentioned characteristic was evaluated. The results are shown in Table 1.
（実施例６）
＜コーティング液の調製＞
　加水分解液Ａの代わりに実施例５で準備した加水分解液Ｂを用いた以外は、実施例１と同様にコーティング液を調製した。実施例６のコーティング液において、ＭｇＦ2微粒子とバインダとの固形分質量比（ＭｇＦ2微粒子：バインダ）は、９０．０：１０．０であった。 (Example 6)
<Preparation of coating solution>
A coating solution was prepared in the same manner as in Example 1 except that the hydrolysis solution B prepared in Example 5 was used instead of the hydrolysis solution A. In the coating liquid of Example 6, the solid mass ratio (MgF 2 fine particles: binder) between the MgF 2 fine particles and the binder was 90.0: 10.0.
＜低反射コーティングの形成＞
　実施例６では、前述の実施例６のコーティング液を用いた以外は、実施例１と同じ手順でガラス板に低反射コーティングを施した。なお、形成された低反射コーティングに対する加熱処理も、実施例１と同様に行われた。熱風乾燥時の、ガラス板の低反射コーティング用塗膜が形成されているガラス面における最高到達温度は２００℃だった。得られた低反射コーティングの厚さは１５０ｎｍであった。得られた低反射コーティング付きガラス物品について、前述の各特性を評価した。その結果を表１に示す。 <Formation of low-reflection coating>
In Example 6, a low reflection coating was applied to the glass plate in the same procedure as in Example 1 except that the coating liquid of Example 6 was used. In addition, the heat processing with respect to the formed low reflection coating was also performed similarly to Example 1. The maximum temperature reached on the glass surface on which the coating film for low reflection coating on the glass plate was formed during hot air drying was 200 ° C. The resulting low reflection coating thickness was 150 nm. About the obtained glass article with a low reflection coating, each above-mentioned characteristic was evaluated. The results are shown in Table 1.
（実施例７）
＜コーティング液の調製＞
　加水分解液Ａ、１－メトキシ－２－プロパノール（溶媒）及びＭｇＦ2微粒子分散液の量を、加水分解液Ａ０．６０ｇ、１－メトキシ－２－プロパノール（溶媒）７．３７ｇ、ＭｇＦ2微粒子分散液１．８ｇに変更し、さらにＴｉＯ2微粒子分散液（「ＳＴＳ－０１」、石原産業株式会社製、平均粒子径１０～３０ｎｍ、アナターゼ型、Ｘ線粒子径７ｎｍ）０．２ｇを添加した以外は、実施例１と同様にコーティング液を調製した。実施例７のコーティング液において、微粒子（ＭｇＦ2微粒子及びＴｉＯ2微粒子との合計）とバインダとの固形分質量比（ＭｇＦ2微粒子＋ＴｉＯ2微粒子：バインダ）は、７９．２：２０．８であった。 (Example 7)
<Preparation of coating solution>
The amount of hydrolyzed liquid A, 1-methoxy-2-propanol (solvent) and MgF 2 fine particle dispersion was 0.60 g of hydrolyzed liquid A, 7.37 g of 1-methoxy-2-propanol (solvent), MgF 2 fine particle dispersed Except that 0.2 g of TiO 2 fine particle dispersion (“STS-01”, manufactured by Ishihara Sangyo Co., Ltd., average particle size 10-30 nm, anatase type, X-ray particle size 7 nm) was added. Prepared a coating solution in the same manner as in Example 1. In the coating liquid of Example 7, the solid content mass ratio of the fine particles (total of MgF 2 fine particles and TiO 2 fine particles) to the binder (MgF 2 fine particles + TiO 2 fine particles: binder) was 79.2: 20.8. It was.
＜低反射コーティングの形成＞
　実施例７では、前述の実施例７のコーティング液を用いた以外は、実施例１と同じ手順でガラス板に低反射コーティングを施した。なお、形成された低反射コーティングに対する加熱処理も、実施例１と同様に行われた。熱風乾燥時の、ガラス板の低反射コーティング用塗膜が形成されているガラス面における最高到達温度は２００℃だった。得られた低反射コーティングの厚さは１７０ｎｍであった。得られた低反射コーティング付きガラス物品について、前述の各特性を評価した。その結果を表１に示す。 <Formation of low-reflection coating>
In Example 7, a low reflection coating was applied to the glass plate in the same procedure as in Example 1 except that the coating liquid of Example 7 was used. In addition, the heat processing with respect to the formed low reflection coating was also performed similarly to Example 1. The maximum temperature reached on the glass surface on which the coating film for low reflection coating on the glass plate was formed during hot air drying was 200 ° C. The resulting low reflection coating thickness was 170 nm. About the obtained glass article with a low reflection coating, each above-mentioned characteristic was evaluated. The results are shown in Table 1.
（比較例１）
＜コーティング液の調製＞
　実施例１で準備した加水分解液Ａ１．０５ｇ、１－メトキシ－２－プロパノール（溶媒）７．８５ｇ、ＳｉＯ2微粒子分散液（「クォートロン　ＰＬ－７」、扶桑化学工業株式会社製、平均粒径１２５ｎｍ、固形分濃度２３質量％）０．８５ｇ、Ａｌ2Ｏ3源（塩化アルミニウム６水和物（シグマアルドリッチ社製、試薬グレード）の５質量％水溶液）０．２５ｇを攪拌混合し、比較例１のコーティング液を得た。比較例１のコーティング液において、ＳｉＯ2微粒子とバインダとの固形分質量比（ＳｉＯ2微粒子：バインダ）は、６１．９：３８．１であった。 (Comparative Example 1)
<Preparation of coating solution>
Hydrolyzate A 1.05 g prepared in Example 1, 7.85 g of 1-methoxy-2-propanol (solvent), SiO 2 fine particle dispersion (“Quatron PL-7”, manufactured by Fuso Chemical Industry Co., Ltd., average particle diameter 125 nm, solid content concentration 23 mass%) 0.85 g, Al 2 O 3 source (5 mass% aqueous solution of aluminum chloride hexahydrate (manufactured by Sigma-Aldrich, reagent grade)) 0.25 g was stirred and mixed, and Comparative Example 1 coating liquid was obtained. In the coating liquid of Comparative Example 1, the solid content mass ratio between the SiO 2 fine particles and the binder (SiO 2 fine particles: binder) was 61.9: 38.1.
＜低反射コーティングの形成＞
　比較例１では、前述の比較例１のコーティング液を用いた以外は、実施例１と同じ手順でガラス板に低反射コーティングを施した。ただし、実施例１とは異なり、形成された低反射コーティングに対する加熱処理は行われなかった。熱風乾燥時の、ガラス板の低反射コーティング用塗膜が形成されているガラス面における最高到達温度は２００℃だった。得られた低反射コーティングの厚さは１５０ｎｍであった。得られた低反射コーティング付きガラス物品について、前述の各特性を評価した。その結果を表１に示す。 <Formation of low-reflection coating>
In Comparative Example 1, a low reflection coating was applied to the glass plate in the same procedure as in Example 1 except that the coating liquid of Comparative Example 1 was used. However, unlike Example 1, the heat treatment for the formed low-reflection coating was not performed. The maximum temperature reached on the glass surface on which the coating film for low reflection coating on the glass plate was formed during hot air drying was 200 ° C. The resulting low reflection coating thickness was 150 nm. About the obtained glass article with a low reflection coating, each above-mentioned characteristic was evaluated. The results are shown in Table 1.
（比較例２）
＜コーティング液の調製＞
　加水分解液Ａ、１－メトキシ－２－プロパノール（溶媒）及びＭｇＦ2微粒子分散液の量を、加水分解液Ａ１．４０ｇ、１－メトキシ－２－プロパノール（溶媒）７．２０ｇ、ＭｇＦ2微粒子分散液１．４０ｇに変更した以外は、実施例１と同様にコーティング液を調製した。比較例１のコーティング液において、ＭｇＦ2微粒子とバインダとの固形分質量比（ＭｇＦ2微粒子：バインダ）は、５０．０：５０．０であった。 (Comparative Example 2)
<Preparation of coating solution>
The amount of hydrolyzed liquid A, 1-methoxy-2-propanol (solvent) and MgF 2 fine particle dispersion was 1.40 g of hydrolyzed liquid A, 7.20 g of 1-methoxy-2-propanol (solvent), MgF 2 fine particle dispersed. A coating solution was prepared in the same manner as in Example 1 except that the solution was changed to 1.40 g. In the coating liquid of Comparative Example 1, the solid content mass ratio (MgF 2 fine particles: binder) between the MgF 2 fine particles and the binder was 50.0: 50.0.
＜低反射コーティングの形成＞
　比較例２では、前述の比較例２のコーティング液を用いた以外は、実施例１と同じ手順でガラス板に低反射コーティングを施した。ただし、実施例１とは異なり、形成された低反射コーティングに対する加熱処理は行われなかった。熱風乾燥時の、ガラス板の低反射コーティング用塗膜が形成されているガラス面における最高到達温度は２００℃だった。得られた低反射コーティングの厚さは１５０ｎｍであった。得られた低反射コーティング付きガラス物品について、前述の各特性を評価した。その結果を表１に示す。 <Formation of low-reflection coating>
In Comparative Example 2, a low reflection coating was applied to the glass plate in the same procedure as in Example 1 except that the coating liquid of Comparative Example 2 was used. However, unlike Example 1, the heat treatment for the formed low-reflection coating was not performed. The maximum temperature reached on the glass surface on which the coating film for low reflection coating on the glass plate was formed during hot air drying was 200 ° C. The resulting low reflection coating thickness was 150 nm. About the obtained glass article with a low reflection coating, each above-mentioned characteristic was evaluated. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例１～７の低反射コーティング付きガラス物品は、最低反射率が２％以下と低く、低反射コーティング形成前後の反射率差（反射率低減効果）が３％以上と高く、かつ透過率ゲインが２．９％以上と高く、非常に優れた光学特性を有していた。さらに、実施例１～７の低反射コーティング付きガラス物品では、摩耗試験後の可視光反射率の低下が３％以下に抑えられており、十分な耐摩耗性も備えていた。また、低反射コーティングがＴｉＯ2微粒子を含んでいる実施例７の低反射コーティング付きガラス物品は、ＵＶ照射後の接触角が５度以下であり、光触媒効果も確認された。 The glass articles with low reflection coating of Examples 1 to 7 have a minimum reflectance as low as 2% or less, a difference in reflectance before and after formation of the low reflection coating (reflectance reduction effect) as high as 3% or more, and a transmittance gain. Was as high as 2.9% or more and had excellent optical characteristics. Further, in the glass articles with low reflection coating of Examples 1 to 7, the decrease in visible light reflectance after the abrasion test was suppressed to 3% or less, and sufficient abrasion resistance was provided. Further, the glass article with a low reflection coating of Example 7 in which the low reflection coating contains TiO 2 fine particles had a contact angle of 5 degrees or less after UV irradiation, and a photocatalytic effect was also confirmed.
　一方、比較例１及び２の低反射コーティング付きガラス物品は、透過率ゲインが低く、光学特性と耐久性とのバランスが良くなかった。 On the other hand, the glass articles with low reflection coating of Comparative Examples 1 and 2 had low transmittance gain, and the balance between optical properties and durability was not good.
　本発明によれば、光学特性に優れた低反射コーティング付きガラス物品を提供できる。 According to the present invention, a glass article with a low reflection coating having excellent optical properties can be provided.

Claims (14)

  1. 　ガラス基材と、前記ガラス基材の表面の少なくとも一部に形成されている低反射コーティングとを含む低反射コーティング付きガラス物品であって、
    　前記低反射コーティングは、微粒子とバインダとからなり、
    　前記微粒子は、主成分としてＭｇＦ2微粒子を含み、
    　前記バインダは、主成分として無機酸化物を含む、
    低反射コーティング付きガラス物品。     A glass article with a low reflection coating comprising a glass substrate and a low reflection coating formed on at least a portion of the surface of the glass substrate,
    The low reflection coating is composed of fine particles and a binder,
    The fine particles include MgF 2 fine particles as a main component,
    The binder contains an inorganic oxide as a main component,
    Glass article with low reflection coating.
  2. 　前記バインダに含まれる前記無機酸化物は、Ｓｉ、Ａｌ、Ｚｒ、Ｔｉ、Ｓｎ及びＦｅからなる群から選ばれる少なくともいずれか１種の金属の酸化物である、
    請求項１に記載の低反射コーティング付きガラス物品。     The inorganic oxide contained in the binder is an oxide of at least one metal selected from the group consisting of Si, Al, Zr, Ti, Sn, and Fe.
    The glass article with a low reflection coating according to claim 1.
  3. 　前記バインダに含まれる前記無機酸化物は、Ｓｉの酸化物とＡｌの酸化物とからなる、
    請求項２に記載の低反射コーティング付きガラス物品。     The inorganic oxide contained in the binder consists of an oxide of Si and an oxide of Al.
    The glass article with a low reflection coating according to claim 2.
  4. 　前記バインダに含まれる前記無機酸化物は、Ａｌの酸化物からなる、
    請求項２に記載の低反射コーティング付きガラス物品。     The inorganic oxide contained in the binder is made of an oxide of Al.
    The glass article with a low reflection coating according to claim 2.
  5. 　前記バインダは、有機成分をさらに含む、
    請求項１～４のいずれか１項に記載の低反射コーティング付きガラス物品。     The binder further includes an organic component.
    The glass article with a low reflection coating according to any one of claims 1 to 4.
  6. 　前記ＭｇＦ2微粒子の平均粒径が、１０～３０ｎｍである、
    請求項１～５のいずれか１項に記載の低反射コーティング付きガラス物品。     The average particle diameter of the MgF 2 fine particles is 10 to 30 nm.
    The glass article with a low reflection coating according to any one of claims 1 to 5.
  7. 　前記低反射コーティングにおける前記微粒子と前記バインダとの質量比（微粒子：バインダ）が、９５：５～３５：６５である、
    請求項１～６のいずれか１項に記載の低反射コーティング付きガラス物品。     The mass ratio of the fine particles to the binder (fine particles: binder) in the low reflection coating is 95: 5 to 35:65.
    The glass article with a low-reflection coating according to any one of claims 1 to 6.
  8. 　前記バインダに含まれる前記無機酸化物において、Ｓｉの酸化物の含有量をＳｉＯ2に換算し、かつＡｌ酸化物の含有量をＡｌ2Ｏ3に換算した場合、ＳｉＯ2とＡｌ2Ｏ3との質量比（ＳｉＯ2：Ａｌ2Ｏ3）が、９９．５：０．５～９７：３である、
    請求項３に記載の低反射コーティング付きガラス物品。     In the inorganic oxide contained in the binder, when the content of Si oxide is converted to SiO 2 and the content of Al oxide is converted to Al 2 O 3 , SiO 2 and Al 2 O 3 The mass ratio (SiO 2 : Al 2 O 3 ) is 99.5: 0.5 to 97: 3,
    The glass article with a low reflection coating according to claim 3.
  9. 　前記低反射コーティングが形成されている面の反射率について、当該反射率が最低となる波長における反射率が２％以下である、
    請求項１～８のいずれか１項に記載の低反射コーティング付きガラス物品。     Regarding the reflectance of the surface on which the low-reflection coating is formed, the reflectance at a wavelength at which the reflectance is lowest is 2% or less.
    The glass article with a low reflection coating according to any one of claims 1 to 8.
  10. 　前記低反射コーティングが形成されている面の波長域３８０～８５０ｎｍにおける平均反射率について、前記低反射コーティングが形成されていない状態の前記面の前記平均反射率から、前記低反射コーティングが形成されている状態の前記面の前記平均反射率を差し引いた差が、３％以上である、
    請求項１～９のいずれか１項に記載の低反射コーティング付きガラス物品。     Regarding the average reflectance in the wavelength range 380 to 850 nm of the surface on which the low-reflection coating is formed, the low-reflection coating is formed from the average reflectance of the surface in the state where the low-reflection coating is not formed. The difference obtained by subtracting the average reflectance of the surface in a state of being 3% or more,
    The glass article with a low reflection coating according to any one of claims 1 to 9.
  11. 　前記低反射コーティングが形成されている面の波長域３８０～８５０ｎｍにおける平均透過率について、前記低反射コーティングが形成されている状態の前記面の前記平均透過率から、前記低反射コーティングが形成されていない状態の前記面の前記平均透過率を差し引いた差が、２．９％以上である、
    請求項１～１０のいずれか１項に記載の低反射コーティング付きガラス物品。     Regarding the average transmittance in the wavelength range of 380 to 850 nm of the surface on which the low-reflection coating is formed, the low-reflection coating is formed from the average transmittance on the surface in the state where the low-reflection coating is formed. The difference obtained by subtracting the average transmittance of the surface in the absence state is 2.9% or more.
    The glass article with a low reflection coating according to any one of claims 1 to 10.
  12. 　前記低反射コーティングが形成されている面の可視光反射率について、テーバー摩耗試験後の可視光反射率から、前記試験前の可視光反射率を差し引いた差が３％以下である、
    請求項１～１１のいずれか１項に記載の低反射コーティング付きガラス物品。     For the visible light reflectance of the surface on which the low-reflection coating is formed, the difference obtained by subtracting the visible light reflectance before the test from the visible light reflectance after the Taber abrasion test is 3% or less.
    The glass article with a low-reflection coating according to any one of claims 1 to 11.
  13. 　前記微粒子は、前記ＭｇＦ2微粒子以外の微粒子をさらに含む、
    請求項１～１２のいずれか１項に記載の低反射コーティング付きガラス物品。     The fine particles further include fine particles other than the MgF 2 fine particles.
    The glass article with a low-reflection coating according to any one of claims 1 to 12.
  14. 　前記ＭｇＦ2微粒子以外の前記微粒子は、ＴｉＯ2微粒子である、
    請求項１３に記載の低反射コーティング付きガラス物品。     The fine particles other than the MgF 2 fine particles are TiO 2 fine particles,
    The glass article with a low-reflection coating according to claim 13.
PCT/JP2018/016160 2017-04-27 2018-04-19 Glass article with low-reflective coating WO2018198935A1 (en)

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JPH05320387A (en) * 1992-05-18 1993-12-03 Hitachi Ltd Method for forming ultra-fine particle film, transparent plate and image-displaying plate
JP2005001900A (en) * 2003-06-09 2005-01-06 Nippon Sheet Glass Co Ltd Substrate coated with low light reflective coating film, its manufacturing method, and composition for the low light reflective coating film
JP2008501557A (en) * 2004-06-08 2008-01-24 ライプニッツ−インスティトゥート フィア ノイエ マテリアーリエン ゲマインニュッツィゲ ゲゼルシャフト ミット ベシュレンクタ ハフトゥンク Abrasion and scratch resistant coating with low refractive index on support
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JP2018049075A (en) * 2016-09-20 2018-03-29 キヤノンファインテックニスカ株式会社 Optical film, substrate including optical film, and optical device including substrate

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