WO2015002042A1 - 太陽電池モジュール用防眩膜、防眩膜付き太陽電池モジュールおよびそれらの製造方法 - Google Patents
太陽電池モジュール用防眩膜、防眩膜付き太陽電池モジュールおよびそれらの製造方法 Download PDFInfo
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- WO2015002042A1 WO2015002042A1 PCT/JP2014/066790 JP2014066790W WO2015002042A1 WO 2015002042 A1 WO2015002042 A1 WO 2015002042A1 JP 2014066790 W JP2014066790 W JP 2014066790W WO 2015002042 A1 WO2015002042 A1 WO 2015002042A1
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- WIPO (PCT)
- Prior art keywords
- inorganic layer
- antiglare film
- solar cell
- inorganic
- fine particles
- Prior art date
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- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- NJWMENBYMFZACG-UHFFFAOYSA-N n-heptylheptan-1-amine Chemical compound CCCCCCCNCCCCCCC NJWMENBYMFZACG-UHFFFAOYSA-N 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- SVEUVITYHIHZQE-UHFFFAOYSA-N n-methylpyridin-2-amine Chemical compound CNC1=CC=CC=N1 SVEUVITYHIHZQE-UHFFFAOYSA-N 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- KPADFPAILITQBG-UHFFFAOYSA-N non-4-ene Chemical compound CCCCC=CCCC KPADFPAILITQBG-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- BZVJOYBTLHNRDW-UHFFFAOYSA-N triphenylmethanamine Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(N)C1=CC=CC=C1 BZVJOYBTLHNRDW-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C09D183/16—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
- H02S40/20—Optical components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/62—Nitrogen atoms
-
- 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
- Y02E10/547—Monocrystalline silicon PV cells
Definitions
- the present invention relates to an antiglare film for a solar cell module formed on a transparent insulating substrate of the solar cell module, and a solar cell module including the antiglare film. Furthermore, this invention relates to the manufacturing method of a solar cell module with an anti-glare film and an anti-glare film.
- a solar cell is a solar cell in which an electromotive force element (solar cell) composed of single crystal silicon, a silicon-based thin film, a compound semiconductor, or the like is sealed with a resin between a front cover glass and a back cover film. Served as a module.
- an electromotive force element solar cell
- a transparent electrode layer, a semiconductor layer, and a second electrode layer are sequentially formed on a transparent insulating substrate such as glass while patterning each layer by a laser scribe method from the light incident side. Substrate-integrated thin film solar cell modules obtained in this way have been proposed.
- the glass substrate has a concavo-convex structure
- thin-film solar cells are integrated by laser scribing
- laser light is scattered by the glass substrate, which makes it difficult to pattern electrode layers and semiconductor layers. Therefore, it is difficult to apply the antiglare method for forming the uneven shape on the glass substrate itself to a thin film solar cell or the like that is integrated by laser scribing.
- an antiglare solar cell module in which a concavo-convex film containing fine particles in a binder (hereinafter referred to as an antiglare film) is formed on the surface of a glass substrate has also been proposed (for example, Patent Document 2 and Patent Document 3).
- an antiglare film is formed by forming a film containing fine particles in an acrylic or urethane organic polymer matrix on the display surface (see, for example, Patent Document 4).
- the method of forming a concavo-convex shape on the glass substrate itself requires a special processing on the glass, so that the versatility is low, such as public facilities, industrial facilities, mega solar, etc. It is only applied to custom-made products for large-scale power generation facilities.
- solar cell modules other than the solar radiation surface for example, the north surface
- An antiglare film as disclosed in Patent Documents 2 and 3 can be formed on a substrate after modularization of a solar cell, and is excellent in versatility.
- the antiglare films disclosed in Patent Documents 2 and 3 are not sufficiently strong in film strength and adhesion to the substrate, and are installed outdoors for a long period of time. It was found to be inferior in durability when exposed to.
- the antiglare films of Patent Documents 2 and 3 require heating at a temperature of 100 ° C. or higher when the binder is cured to form the antiglare film. Therefore, when the antiglare film is formed after modularizing the solar battery, thermal deterioration of the solar battery cell provided on the substrate may occur due to heating for curing.
- the solar cell module when the solar cell module is installed outdoors, contaminants such as dust and pollen accumulated on the light receiving surface may block the light, resulting in a decrease in conversion efficiency due to a reduction in the amount of incident light. Therefore, in order to maintain the conversion efficiency in actual use, it is desired that the solar cell module has dirt on the light receiving surface flowing down due to rain or the like.
- the antiglare solar cell module has a problem that contaminants are likely to enter the surface irregularities, and the removal of deposited contaminants is low.
- the present invention provides an antiglare film for a solar cell module that is excellent in adhesion and strength to a substrate, and excellent in the removal of contaminants deposited and adhered on a light receiving surface, and the antiglare film. It aims at provision of a solar cell module provided with a glare film.
- the present invention relates to an antiglare film for a solar cell module and a method for producing the same.
- the antiglare film of the present invention is used by being formed on a transparent insulating substrate of a solar cell module.
- the antiglare film has a first inorganic layer and a second inorganic layer in this order from the substrate side.
- the first inorganic layer contains transparent spherical inorganic fine particles in an inorganic binder.
- the first inorganic layer is preferably a continuous film having no cracks.
- the inorganic binder in the first inorganic layer is preferably composed mainly of silicon oxide containing Si—O bonds obtained by hydrolysis of Si—H bonds and Si—N bonds.
- the second inorganic layer contains an inorganic binder.
- the inorganic binder in the second inorganic layer is not particularly limited, but is preferably a silicon oxide containing Si—O bonds as a main component obtained by hydrolysis of Si—H bonds and Si—N bonds.
- the average thickness d 1 of the first inorganic layer is preferably 500 nm ⁇ 2000 nm
- the average thickness d 2 of the second inorganic layer is preferably 50 nm ⁇ 1000 nm.
- the ratio d 2 / d 1 between the average thickness of the first inorganic layer and the average thickness of the second inorganic layer is preferably 0.025 to 0.5.
- the inorganic fine particles in the first inorganic layer preferably have an average primary particle diameter calculated from cross-sectional observation of the antiglare film of 0.1 ⁇ m to 5.0 ⁇ m.
- the inorganic fine particles in the first inorganic layer are, for example, silica fine particles containing SiO 2 as a main component.
- the first inorganic layer may further contain a pigment or a dye.
- a colored antiglare film can be obtained by having a dye or a pigment in the first inorganic layer.
- the maximum height Ry 2 on the second inorganic layer side surface is preferably 1.0 ⁇ m to 10 ⁇ m.
- the maximum height Ry 2 of the second inorganic layer is preferably smaller than the maximum height Ry 1 at the interface between the first inorganic layer and the second inorganic layer.
- the antiglare film of the present invention preferably has an arithmetic average roughness Ra 2 on the second inorganic layer side surface of 0.25 ⁇ m to 2 ⁇ m and an uneven period Sm 2 of 1 ⁇ m to 30 ⁇ m.
- the ratio Ry 2 / d between the total average film thickness d of the antiglare film and the maximum height Ry 2 of the surface on the second inorganic layer side of the antiglare film is preferably in the range of 1-20. .
- the average refractive index n2 of the second inorganic layer is preferably smaller than the average refractive index n1 of the first inorganic layer. If n 1 > n 2 , the refractive index increases stepwise along the light incident direction from the light receiving surface side of the antiglare film to the substrate side of the solar cell module. Therefore, reflection at the interface is reduced, the amount of light taken into the solar cell module is increased, and the conversion characteristics (particularly short-circuit current density) of the solar cell module can be improved.
- the average primary particle diameter of the particles calculated from the cross-sectional observation of the antiglare film is preferably 10 nm to 300 nm.
- the average primary particle size of the inorganic fine particles in the second inorganic layer is preferably smaller than the average primary particle size of the inorganic fine particles in the first inorganic layer.
- Examples of the low refractive index inorganic fine particles contained in the second inorganic layer include hollow fine particles.
- hollow colloidal silica is preferably used.
- the antiglare film is preferably a first coating step in which a first coating liquid is applied to one main surface of a transparent insulating substrate; a second coating liquid is applied on the coating film of the first coating liquid. A second coating step to be applied; and a curing step in which the first coating liquid and the solvent in the second coating liquid are dried and the coating film is cured. Both the first application step and the second application step are preferably performed by a spray method.
- the first coating liquid preferably contains 0.01 to 20% by weight of transparent spherical inorganic fine particles having an average primary particle size of 0.1 to 5.0 ⁇ m, 0.1 to 20% by weight of polysilazane, and a solvent. Used.
- the second coating solution a solution containing 0.1 to 20% by weight of polysilazane and a solvent is preferably used.
- the second coating solution may further contain 0.01 to 20% by weight of inorganic fine particles having an average primary particle size of 10 nm to 300 nm.
- the solar cell module of the present invention includes at least one solar battery cell on the first main surface of the transparent insulating substrate, and includes the antiglare film on the second main surface of the transparent insulating substrate.
- the solar battery cell is, for example, a thin film solar battery cell.
- Thin film solar cells may be integrated.
- the first electrode layer, the photoelectric conversion unit, and the second electrode layer are provided from the transparent insulating substrate side, and each of these layers is divided into a plurality of cells by providing a linear separation groove.
- An integrated thin film solar cell module that is electrically connected in series or in parallel is exemplified.
- the solar battery cell may be a crystalline silicon solar battery cell including a crystalline silicon substrate.
- the antiglare film can be patterned.
- the solar cell module may have an anti-glare region where an anti-glare film is formed on the substrate and a non-glare region where no anti-glare film is formed.
- Such a pattern anti-glare film can be formed by forming an anti-glare film in an area where no mask is attached after a covering step in which a mask material is attached to a part of the surface of the transparent insulating substrate. .
- an antiglare film is formed on the second main surface of the transparent insulating substrate after the cell forming step in which the solar cells are formed on the first main surface of the transparent insulating substrate. It is preferable that an anti-glare film forming process is performed. For example, after the cell formation process is performed indoors, the substrate after the cell formation is carried out outdoors, and the antiglare film formation process is performed outdoors. In this case, the antiglare film can be formed on the second main surface of the transparent insulating substrate by a spray method.
- an antiglare film forming step is performed after the cell forming step.
- the separation groove is formed by irradiating laser light from the second main surface side of the transparent insulating substrate. According to this method, integration by laser light irradiation is performed through the substrate before the formation of the antiglare film, so that a problem such as a laser scattering by the antiglare film does not occur.
- an antiglare film for a solar cell module having high antiglare properties and excellent adhesion to a substrate and film strength can be obtained.
- the antiglare film according to the present invention has excellent surface removability of contaminants adhered to the surface while having surface irregularities suitable for antiglare properties. Therefore, even when contaminants accumulate and adhere to the light receiving surface of the solar cell module, the contaminants easily flow down due to rain or the like, and a reduction in conversion efficiency in actual use is suppressed.
- FIG. 1 is a cross-sectional view showing a schematic configuration of an antiglare film for a solar cell module according to an embodiment of the present invention, and an antiglare film 50 is formed on a transparent insulating substrate 1.
- the antiglare film 50 has surface irregularities.
- sunlight reflected on the surface of the solar cell module is irregularly reflected in an unspecified direction.
- the scattered light that has been irregularly reflected is not a parallel light beam but is blurred as a whole, so that light pollution due to the reflected light is suppressed.
- the antiglare film 50 has the first inorganic layer 10 and the second inorganic layer 20 from the transparent insulating substrate 1 side.
- the first inorganic layer 10 contains transparent inorganic fine particles 12 in an inorganic binder 11.
- the second inorganic layer 20 contains an inorganic binder 21. Since the first inorganic layer 10 has inorganic fine particles, random irregularities are formed on the surface of the antiglare film 50. Therefore, the incident light to the solar cell module is irregularly reflected on the light receiving surface (interface between the antiglare film 50 and air), and the antiglare property is exhibited. Moreover, by having the 2nd inorganic layer 20 on the 1st inorganic layer 10, the surface shape (especially height difference) of the 1st inorganic layer 10 is relieve
- the first inorganic layer 10 contains transparent inorganic fine particles 12 in an inorganic binder 11.
- silicon oxide is preferably used, and among them, silicon oxide containing Si—O bonds obtained by hydrolysis of Si—H bonds and Si—N bonds is preferable. Used for.
- the silicon oxide contains Si—O bond by hydrolysis of Si—H bond or Si—N bond, in addition to the high transparency of the binder, adhesion with a transparent insulating substrate such as glass, Excellent light resistance and hardness.
- the present inventors formed an antiglare film using a sol-gel material such as a partially hydrolyzed condensate of alkyl silicate, which has been conventionally proposed as a binder material for an antiglare film
- a sol-gel material such as a partially hydrolyzed condensate of alkyl silicate
- the obtained silicon oxide A large number of cracks occurred in the material film, and it was inferior in hardness and durability. This is due to the stress of the interface between the transparent insulating substrate (glass plate) and the antiglare film due to the shrinkage of the material when silicon oxide is formed by reaction hardening and the influence of subsequent heat and moisture. was estimated to have occurred.
- the inorganic layer 10 is easily formed.
- alkyl silicate or the like is used as the binder material for the antiglare film
- an external force such as frictional force is applied to the antiglare film
- fine particles are peeled off from the surface of the antiglare film.
- the film thickness of the first inorganic layer is increased for the purpose of firmly fixing the fine particles in the film, there is a problem that the surface unevenness reflecting the shape of the fine particles is hardly formed and the antiglare property is lowered.
- the shape of the interface between the fine particles and the binder is indefinite, cracks tend to be generated starting from the interface.
- silicon oxide containing Si—O bonds obtained by hydrolysis of Si—H bonds and Si—N bonds can firmly fix fine particles having a large particle diameter in the film. It is possible to form an antiglare film having excellent friction resistance and no cracks.
- spherical fine particles are preferably used as the inorganic fine particles 12 contained in the first inorganic layer 10.
- the particles are spherical, the convex portions on the surface of the film have a curved shape, and the unevenness of the irregularities becomes gentle, so that the entry of contaminants such as dust and pollen into the irregular structure on the surface of the antiglare film is suppressed.
- the “spherical” fine particles are not necessarily true spheres, and may be flat as long as the surface is curved.
- the material of the inorganic fine particles 12 examples include silicon oxide (SiO 2 ), titanium oxide (TiO 2 ), aluminum oxide (Al 2 O 3 ), zirconium oxide (ZrO 2 ), indium tin oxide (ITO), and magnesium fluoride (MgF). 2 ) etc. are preferred.
- the inorganic fine particles 12 are preferably made of a material having a refractive index difference close to that of the binder 11. Therefore, as the fine particles 12, those having silicon oxide as a main component are most preferably used.
- the inorganic fine particles 12 in the first inorganic layer are preferably non-hollow fine particles.
- the inorganic fine particles 12 in the first inorganic layer 10 preferably have a primary average particle diameter of 0.1 ⁇ m to 5.0 ⁇ m, more preferably 0.5 ⁇ m to 4.0 ⁇ m, and 1.0 ⁇ m to More preferably, it is 3.0 ⁇ m. If the particle size of the inorganic fine particles 12 contained in the first inorganic layer 10 is in the above range, surface irregularities suitable for irregular reflection of visible light are formed on the surface of the first inorganic layer 10, and the irregular pattern is prevented. The surface of the glare film 50 is inherited. Therefore, the antiglare property of the solar cell module is improved.
- the primary average particle diameter of the fine particles is calculated from the average value obtained by obtaining the particle diameter of each particle from the cross-sectional observation image of the antiglare film.
- the particle diameter of each particle is defined by the diameter of a circle having the same area as the projected area of the particle (projected area circle equivalent diameter, Heywood diameter).
- the content of the inorganic fine particles 12 in the first inorganic layer 10 is preferably 10 to 200 parts by weight, more preferably 20 to 100 parts by weight, and more preferably 40 to 80 parts by weight with respect to 100 parts by weight of the binder. Part is more preferred.
- the maximum height Ry 2 of the surface of the second inorganic layer 20 formed thereon increases, and the light scattering property on the surface of the antiglare film 50 tends to be improved.
- the relative content of the fine particles 12 is excessively large, the hardness of the first inorganic layer may be lowered or the fine particles may not be firmly fixed.
- the average film thickness d 1 of the first inorganic layer 10 is preferably 500 nm to 2000 nm, more preferably 750 nm to 1750 nm, and even more preferably 1000 nm to 1500 nm. If the thickness d 1 is 500nm or more, it is possible to firmly adhere the inorganic fine particles 12 primary average particle size of greater than 100nm in the substrate surface. Further, if the film thickness d 1 is 2000 nm or less, the surface of the first inorganic layer 10 is formed with unevenness following the shape of the fine particles 12, and the uneven pattern following this is formed on the surface of the antiglare film 50. Therefore, antiglare property is improved.
- the average film thickness d 1 can be calculated from the solid content concentration of the coating liquid, the coating amount, and the coating area.
- the maximum height Ry 1 of the surface of the first inorganic layer 10 is preferably 1 ⁇ m to 10 ⁇ m, more preferably 3 ⁇ m to 8 ⁇ m, and even more preferably 4 ⁇ m to 6 ⁇ m.
- the arithmetic average roughness Ra 1 of the surface of the first inorganic layer 10 is preferably 0.25 ⁇ m to 2 ⁇ m, and preferably 0.3 ⁇ m to 1.5 ⁇ m. More preferably, 0.5 ⁇ m to 1.25 ⁇ m is more preferable, and 0.75 ⁇ m to 1 ⁇ m is even more preferable.
- the uneven period Sm 1 on the surface of the first inorganic layer 10 is preferably 1 ⁇ m to 30 ⁇ m, more preferably 5 ⁇ m to 25 ⁇ m, and even more preferably 10 ⁇ m to 20 ⁇ m.
- the concave / convex cycle Sm is an average value of intervals between peak-valley cycles obtained from an intersection where a roughness curve obtained by a laser microscope intersects an average line.
- the maximum height Ry is a value represented by the distance between the peak line and the valley line of the extracted portion of a roughness curve obtained by a laser microscope by extracting a reference length (0.8 m) in the direction of the average line. .
- the maximum height Ry, the arithmetic average roughness Ra, and the unevenness period Sm are measured in accordance with JIS B0601-1994 unless otherwise specified.
- the arithmetic average roughness Ra and the uneven period Sm can be adjusted by changing the content of the fine particles with respect to the binder and the particle diameter of the fine particles, for example. As the particle size of the fine particles increases, the arithmetic average roughness Ra tends to increase, and as the content of the fine particles increases, the unevenness period Sm tends to decrease.
- the ratio Ry 1 / d 1 between the film thickness d 1 and the maximum height Ry 1 of the first inorganic layer 10 is preferably 1 or more.
- Ry 1 / d 1 being 1 or more means that the surface unevenness of the first inorganic layer is greater than or equal to the average film thickness, and has surface unevenness that is more undulating than the film thickness. Means.
- the first inorganic layer 10 since the first inorganic layer 10 has undulating surface irregularities, and the irregular pattern is inherited by the second inorganic layer surface, a high irregular reflection effect is obtained on the surface of the antiglare film 50.
- Ry 1 / d 1 is preferably 1 to 20, more preferably 1.5 to 16, and further preferably 2 to 12.
- a method for forming the first inorganic layer 10 on the transparent insulating substrate 1 is not particularly limited, but a method of applying a solution containing a silicon oxide binder or a precursor thereof and fine particles on the transparent insulating substrate 1 is suitable. ing.
- the coating method include a dipping method, a spin coating method, a bar coating method, a die coating method, a roll coating method (printing method), a flow coating method, and a spray method.
- the spray method is preferable because it does not require special equipment and an anti-glare film can be easily formed on the insulating substrate even after sealing the cell or installing the module on a roof or the like.
- a polymer containing Si—H bond and Si—N bond is preferably used as the silicon oxide precursor contained in the coating liquid for forming the first inorganic layer 10.
- Polysilazane is preferred as the polymer containing Si—H bonds and Si—N bonds.
- Polysilazane is a polymer whose basic unit is a Si—N bond (silazane bond). It is a material that reacts with moisture in the atmosphere to hydrolyze Si—H bonds and Si—N bonds and convert them into SiO 2. is there.
- Polysilazanes include perhydropolysilazanes that do not have an organic group in the molecule and are composed of repeating basic units represented by — [SiH 2 —NH] —, and a part of alkyl bonded to hydrogen bonded to silicon and / or nitrogen. And organopolysilazane substituted with an organic group such as a group.
- perhydropolysilazane is preferably used from the viewpoint of increasing the content of Si—O bonds derived from Si—H bonds and obtaining an antiglare film having excellent adhesion and strength. Further, a mixture of perhydropolysilazane and organopolysilazane may be used.
- the Si—O bond is obtained by hydrolysis of the Si—H bond, that there is a peak near 2160 cm ⁇ 1 derived from the Si—H bond in the infrared spectrum immediately after application of the binder material, and together with the peak decreases over time or lost, around 1060 cm -1 derived from Si-O bond it can be confirmed by a peak around 800 cm -1 and around 450 cm -1 appearance, increases.
- the Si—O bond can be obtained by the hydrolysis of the Si—N bond, indicating that there is a peak near 840 cm ⁇ 1 derived from the Si—N bond in the infrared spectrum immediately after application of the binder material.
- the binder material is a hydrolysis-cured product of perhydropolysilazane (— [SiH 2 —NH] n —), in addition to the above, the peak near 3370 cm ⁇ 1 derived from the NH bond decreases with time. ⁇ Disappear.
- a coating solution containing 0.01 to 20% by weight of inorganic fine particles, 0.1 to 20% by weight of polysilazane and a solvent is preferably used.
- the solvent those that dissolve polysilazane and are excellent in dispersibility of inorganic fine particles are preferably used, and xylene, dibutyl ether, and the like are particularly preferably used.
- the solid concentration of polysilazane in the coating solution is preferably 0.1% by weight to 20% by weight, more preferably 1% by weight to 10% by weight, and further preferably 2% by weight to 5% by weight.
- the coating solution has a solution viscosity suitable for coating by a spray method or the like, and an inorganic layer having a thickness of 0.5 ⁇ m or more can be stably formed.
- the concentration of the inorganic fine particles in the coating solution is preferably 0.01% by weight to 20% by weight, more preferably 0.1% by weight to 10% by weight, and further preferably 1% by weight to 5% by weight. If the fine particle concentration in the coating solution is within the above range, the fine particles are appropriately dispersed in the polysilazane, and an antiglare film having excellent antiglare properties can be easily obtained.
- spherical fine particles having a primary particle diameter of about 1 ⁇ m are aggregated in air and in solution to form secondary particles.
- the fine particles used in the coating solution preferably have an average secondary particle size of 0.1 ⁇ m to 10 ⁇ m, more preferably 0.5 ⁇ m to 7.5 ⁇ m, and even more preferably 1 ⁇ m to 5 ⁇ m.
- the average secondary particle diameter of the fine particles is measured by a dynamic light scattering method.
- polysilazane is excellent in embedding in fine gaps, and therefore can penetrate into fine gaps between primary particles even when fine particles are aggregated. Therefore, it is possible to form the inorganic layer 10 having a continuous film which is excellent in adhesion between the transparent insulating substrate 1 and the binder 11 and the inorganic fine particles 12 and has no cracks.
- the coating liquid used for forming the first inorganic layer 10 may contain components other than the binder, fine particles and solvent.
- a catalyst can be contained in the coating solution.
- the catalyst examples include 1-methylpiperazine, 1-methylpiperidine, 4,4′-trimethylenedipiperidine, 4,4′-trimethylenebis (1-methylpiperidine), diazabicyclo- [2,2,2] octane, Cis-2,6-dimethylpiperazine, 4- (4-methylpiperidine) pyridine, pyridine, dipyridine, ⁇ -picoline, ⁇ -picoline, ⁇ -picoline, piperidine, lutidine, pyrimidine, pyridazine, 4,4'-trimethylene N-heterocyclic compounds such as dipyridine, 2- (methylamino) pyridine, pyrazine, quinoline, quinoxaline, triazine, pyrrole, 3-pyrroline, imidazole, triazole, tetrazole, 1-methylpyrrolidine; methylamine, dimethylamine, trimethylamine , Ethylamine, diethylamine, tri Tylamine, propyl
- organic acids include acetic acid, propionic acid, butyric acid, valeric acid, maleic acid, stearic acid, and inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrogen peroxide, chloric acid, hypochlorous acid, etc. Is mentioned.
- the metal carboxylate has the formula: (RCOO) nM [wherein R represents an aliphatic group or an alicyclic group and has 1 to 22 carbon atoms, and M represents Ni, Ti, Pt, Rh, Co.
- the metal carboxylate may be an anhydride or a hydrate.
- An acetylacetona complex is a complex in which an anion generated by acid dissociation from acetylacetone (2,4-pentadione) is coordinated to a metal atom, and generally has the formula (CH 3 COCHCOCH 3 ) n M [wherein , M represents an n-valent metal. ] Is represented.
- Suitable metals M include, for example, nickel, platinum, palladium, aluminum, rhodium and the like.
- organic metal compounds such as peroxide, metal chloride, ferrocene, zirconocene, and the like can also be used.
- the content of the catalyst in the coating solution is preferably about 0.5 to 10 parts by weight with respect to 100 parts by weight of polysilazane.
- a colored anti-glare film can also be formed by adding a pigment or a dye to the coating liquid used for forming the first inorganic layer 10.
- the kind of the pigment or dye is not particularly limited, but the pigment is preferably one that can be well dispersed in the solvent of the coating solution, and the dye is preferably one that dissolves in the solvent of the coating solution.
- the particle diameter of the pigment is preferably small, and preferably about 50 nm to 200 nm.
- the content of the dye or pigment varies depending on the color to be colored, the type of the dye / pigment, and the like. For example, about 30 to 60 parts by weight with respect to 100 parts by weight of the solid content of the first inorganic layer. preferable.
- a color solar cell module as shown in FIG. 4 can be produced, and the design of the module can be improved, The variation of can be expanded. Moreover, since the 1st inorganic layer 10 has microparticles
- an appropriate method such as a spray method can be employed as described above.
- Polysilazane can be cured even at room temperature and normal pressure. Therefore, it can be said that the spray method in which the coating solution can be stored in a sealed state until just before use is a coating method with excellent productivity.
- the wettability of the substrate surface can also be improved by performing alkali cleaning, celico cleaning, or the like on the substrate surface before applying the coating liquid to the transparent insulating substrate 1.
- surface treatment of the transparent insulating substrate may be performed.
- polysilazane is excellent in adhesion (affinity) with glass and has a high embedding property in fine gaps. Therefore, in the present invention, pretreatment for increasing the wettability of the substrate surface is performed. It may be omitted.
- a base layer (not shown) may be provided between the transparent insulating substrate 1 and the first inorganic layer 10.
- a polysilazane coating film having a film thickness of about 1 nm to 200 nm is formed by a spray method, thereby improving the adhesion between the transparent insulating substrate 1 and the first inorganic layer 10.
- the underlayer may contain transparent fine particles having a particle size smaller than that of the fine particles 12 in the first inorganic layer 10 (for example, a particle size of about several tens to several hundreds of nm).
- the solvent of the coating solution is dried and the polysilazane is cured to form the first inorganic layer.
- both the drying of the solvent in the coating solution and the curing of the polysilazane are performed at 80 ° C. or lower. . If drying and curing are performed at such a low temperature, it is possible to suppress a decrease in power generation characteristics due to thermal deterioration of the amorphous silicon semiconductor or the like in the solar battery cell.
- drying and curing are preferably performed at normal temperature and normal pressure.
- drying and curing are preferably performed at room temperature and normal pressure from the viewpoint of facilitating the formation of the antiglare film.
- the normal temperature / normal pressure refers to an environment in which no artificial heating, pressurization / depressurization from the outside is performed as in a normal outdoor environment.
- the first inorganic layer 10 having excellent adhesion to the substrate and high hardness is formed on the transparent insulating substrate 1.
- the first inorganic layer 10 is preferably a continuous film having no cracks. “No crack” means that 5 points are randomly extracted from the 10 cm square area of the film surface, and a 5000 times SEM plane observation is performed. It refers to something that is not.
- a second inorganic layer 20 is formed on the first inorganic layer 10.
- the second inorganic layer 20 contains a binder 21.
- the binder 21 constituting the second inorganic layer 20 is preferably a material excellent in adhesiveness with the first inorganic layer 10, and an inorganic binder is suitably used.
- the inorganic binder 21 is not particularly limited as long as it has transparency, but a silicon-based compound is preferably used. Specific examples of silicon compounds include tetramethyl silicate, tetraethyl silicate, tetra-n-propyl silicate, tetra-i-propyl silicate, tetra-n-butyl silicate, tetra-i-butyl silicate, and tetra-t-butyl silicate.
- Tetraalkyl silicates such as: methyltrimethoxysilane, methyltriethoxysilane, octadecyltriethoxysilane, methyltri-sec-octyloxysilane, methyltriisopropoxysilane, alkyltrialkoxysilane such as methyltributoxysilane, phenyltrimethoxysilane , Aryltrialkoxysilanes such as phenyltriethoxysilane, alkyltriaryloxysilanes such as methyltriphenoxysilane, 3-glycidoxypropyltrimethoxy Trialkoxysilane or triaryl silane such as glycidoxy trialkoxysilane such as silane.
- the binder 21 in the second inorganic layer 20 can be used by mixing two or more kinds of compounds.
- the inorganic binder may be one in which organic molecules are added into the inorganic binder molecular structure, one in which inorganic molecules and organic molecules are mixed, or one in which the organic binder is dispersed in the inorganic binder. .
- silicon oxide is preferable like the binder 11 of the first inorganic layer 10. If the binder 11 of the first inorganic layer and the binder 21 of the second inorganic layer are the same material, the adhesion at the interface is excellent, and the detachment of the fine particles 12 in the first inorganic layer 10 is prevented. Since it can contribute, it is easy to obtain a high-strength film.
- the second inorganic layer 20 is preferably curable at a low temperature, more preferably at normal temperature and pressure. Therefore, the second inorganic layer binder 21 is particularly preferably a silicon oxide containing Si—O bonds formed by hydrolysis of Si—H bonds or Si—N bonds using polysilazane as a precursor material.
- the average film thickness d2 of the second inorganic layer 20 is preferably 50 nm to 1000 nm, more preferably 75 nm to 750 nm, and further preferably 100 nm to 500 nm.
- the average thickness d 1 and a ratio d 2 / d 1 between the average thickness d 2 of the second inorganic layer 20 of the first inorganic layer 10 is preferably 0.025-0.5, 0.04 To 0.4 is more preferable, and 0.06 to 0.3 is more preferable.
- the thickness d 2 is in the above range, the surface of the second inorganic layer 20, namely the light-receiving surface side surface of the anti-glare film 50 while maintaining the uneven shape pattern of the first inorganic layer 10, a first The sudden shape change on the surface of the inorganic layer 10 is filled with the second inorganic layer 20 and alleviated. Therefore, the antiglare film 50 having an antiglare property due to the uneven shape and excellent in the removal of contaminants can be obtained.
- the film thickness d 2 of the second inorganic layer 20 is preferably 0.025 to 0.8 times the average primary particle size of the fine particles 12 in the first inorganic layer 10, preferably 0.04 times. It is more preferably 0.7 times, more preferably 0.06 times to 0.6 times.
- the film thickness d 2 is solid concentration of the coating solution can be calculated from the coating weight and coating area.
- the maximum height Ry 2 of the surface of the second inorganic layer 20 is preferably 1 ⁇ m to 8 ⁇ m, more preferably 1.3 ⁇ m to 7 ⁇ m, further preferably 1.5 ⁇ m to 6 ⁇ m, particularly preferably 1.7 ⁇ m to 4 ⁇ m, and 2 ⁇ m. Most preferred is ⁇ 3 ⁇ m.
- the maximum height Ry 2 of the second inorganic layer side surface is smaller than the maximum height Ry 1 at the surface of the first inorganic layer 10, that is, at the interface between the first inorganic layer 10 and the second inorganic layer 20. It is preferable.
- Ry 1 Ry 2 tends to be smaller than Ry 1 and the ratio Ry 2 / Ry 1 and Ry 2 is preferably about 0.3 to 0.95, and more preferably 0.4-0.9, more preferably 0.5-0.8.
- the ratio Ry 2 / d between the total average film thickness d of the antiglare film 50 and the maximum height Ry 2 is preferably 0.8 to 10, more preferably 1 to 8, and further preferably 1.2 to 6. preferable.
- the arithmetic average roughness Ra 2 on the surface of the second inorganic layer 20 is preferably 0.1 ⁇ m to 1.5 ⁇ m, preferably 0.15 ⁇ m to 1. 2 ⁇ m is more preferable, 0.2 ⁇ m to 1 ⁇ m is further preferable, and 0.25 ⁇ m to 0.8 ⁇ m is particularly preferable.
- the uneven period Sm 2 on the surface of the second inorganic layer 20 is preferably 1 ⁇ m to 30 ⁇ m, more preferably 5 ⁇ m to 25 ⁇ m, and even more preferably 10 ⁇ m to 20 ⁇ m.
- the antiglare film 50 reduces the entry of contaminants to the surface while maintaining the antiglare property.
- the average refractive index n 2 of the second inorganic layer 20 is preferably smaller than the average refractive index n 1 of the first inorganic layer 10.
- the difference between n 2 and n 2 is preferably 0.03 or more, more preferably 0.05 or more, still more preferably 0.07 or more, and particularly preferably 0.10 or more.
- the average refractive index n 1 of the first inorganic layer 10 mainly made of silicon oxide is about 1.45 to 1.55, whereas the average refractive index n 2 of the second inorganic layer 20 is 1. 45 or less is preferable and 1.40 or less is more preferable.
- the second inorganic layer has a lower refractive index by containing inorganic fine particles 22 having a lower refractive index than that of the binder 21 in the second inorganic layer 20.
- the difference between the refractive index of the binder 21 and the refractive index of the fine particles 22 is preferably 0.05 or more, more preferably 0.10 or more, and further preferably 0.13 or more.
- the average primary particle diameter calculated from the cross-sectional observation of the antiglare film is preferably 10 nm to 300 nm, more preferably 20 nm to 150 nm, and further preferably 30 nm to 100 nm. preferable.
- the average primary particle size of the inorganic fine particles 22 in the second inorganic layer 20 is the average of the inorganic fine particles 12 in the first inorganic layer 10. It is preferably smaller than the primary particle size.
- the particle size of the fine particles 22 in the second inorganic layer 20 is 300 nm or less, the particle size is smaller than the main wavelength range of sunlight, so that light is refracted / reflected / scattered at the interface between the binder 21 and the fine particles 22. Is suppressed. Therefore, the refractive index of the second inorganic layer 20 is lowered, and loss due to reflection / scattering of the light incident on the antiglare film 50 is reduced.
- the particle diameter of the fine particles 22 is 10 nm or more, the fine particles 22 can be favorably dispersed in the second inorganic layer 20.
- the material of the fine particles 22 in the second inorganic layer 20 is not particularly limited as long as the refractive index is lower than that of the binder 21.
- a metal fluoride such as magnesium fluoride can be used assuming that the material itself has a low refractive index.
- hollow particles can also be used as the low refractive particles. Since the hollow particles have an intermediate refractive index between the constituent material and air, they are suitable for lowering the refractive index.
- hollow silica particles are preferable from the viewpoint of dispersibility in the film and strength, and among them, hollow colloidal silica particles are preferably used.
- the content is not particularly limited, but from the viewpoint of achieving a low refractive index, the amount is preferably 10 parts by weight or more with respect to 100 parts by weight of the binder, 30% by weight. More preferably, the amount is more preferably 40 parts by weight or more.
- the upper limit of the content of the fine particles 22 is not particularly limited, but if the relative content of the fine particles 22 is excessively large, the hardness of the second inorganic layer may be lowered or the fine particles may not be firmly fixed. Therefore, the content of the fine particles 22 is preferably 300 parts by weight or less, more preferably 200 parts by weight or less, and further preferably 150 parts by weight or less with respect to 100 parts by weight of the binder.
- a method for forming the second inorganic layer 20 on the first inorganic layer 10 is not particularly limited, but a coating method such as a spray method is preferable as in the formation of the first inorganic layer 10.
- the coating solution for forming the second inorganic layer 20 a solution containing a binder 21 or a precursor thereof and a solvent for dissolving the binder 21 is used. Further, when the second inorganic layer 20 contains the fine particles 22, it is preferable that the fine particles are contained in the coating solution. In order to suppress aggregation of the fine particles, the fine particles 22 are preferably added to the coating liquid in a state of being dispersed in the dispersant.
- the fine particle dispersant examples include organic solvents such as methyl ethyl ketone, tetrahydrofuran, dimethyl sulfoxide, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether, or mixtures thereof.
- organic solvents such as methyl ethyl ketone, tetrahydrofuran, dimethyl sulfoxide, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether, or mixtures thereof.
- the solid content concentration of the binder or its precursor in the coating solution for forming the second inorganic layer 20 is preferably 0.1% by weight to 20% by weight, more preferably 1% by weight to 10% by weight. More preferred is 5% by weight.
- the coating solution has a solution viscosity suitable for coating by a spray method or the like if the solid content concentration is in the above range.
- the concentration of the inorganic fine particles in the coating solution is appropriately determined according to the content ratio of the binder 21 and the fine particles 22 in the second inorganic layer 20.
- the coating liquid used for forming the second inorganic layer 20 may contain a catalyst, a pigment, a dye, etc. in addition to the binder, fine particles and solvent.
- the coating solution onto the first inorganic layer 10 an appropriate method such as a spray method can be adopted as described above. Since the first inorganic layer 10 and the second inorganic layer 20 can be formed subsequently, it is preferable that both the first inorganic layer and the second inorganic layer are formed by a spray method.
- the first inorganic layer may be before curing, during curing, or after curing.
- the first inorganic layer is formed by application of the polysilazane solution and curing is performed at room temperature, curing starts immediately after application, but Si—H bonds and Si—N bonds are hydrolyzed and almost all bonds are formed. It takes several days to several weeks before the conversion to Si-O. Therefore, from the viewpoint of improving the productivity of the antiglare film, it is preferable that application for forming the second inorganic layer is performed before or during the curing of the first inorganic layer.
- the curing of the first inorganic layer and the curing of the second inorganic layer are performed in parallel. Then proceed. Therefore, the adhesiveness at the interface between the first inorganic layer 10 and the second inorganic layer 20 tends to be improved.
- the antiglare film 50 obtained in this way reflects light irregularly due to the random surface irregularity formed by the fine particles 12 in the first inorganic layer 10 and exhibits antiglare properties. Moreover, since the surface shape (especially height difference) of the 1st inorganic layer 10 is relieve
- the pencil hardness by the pencil hardness test (JIS K5600) of the anti-glare film 50 is preferably 3H or more, more preferably 5H or more, and further preferably 6H or more.
- FIG. 3 is a cross-sectional view illustrating a schematic configuration of a thin-film solar cell module with an antiglare film according to one embodiment.
- This solar cell module includes a transparent insulating substrate 1 and solar cells 5 formed on the first main surface of the transparent insulating substrate 1, and includes an antiglare film 50 on the second main surface of the translucent substrate. .
- the solar battery cell 5 includes the first electrode layer 2, the photoelectric conversion unit 3, and the second electrode layer 4 from the transparent insulating substrate 1 side.
- the solar battery cell 5 is separated into a plurality of regions, and each region is electrically connected in series with each other.
- the filling resin 6 and the back surface sealing plate 7 are provided on the second electrode layer 4.
- the solar cell thus sealed is attached with a frame 8 used to hold the transparent insulating substrate 1, the filling resin 6, the back surface sealing plate 7 and the like, and to be attached to a frame such as a roof. ing.
- the embodiment relating to the thin film solar cell module shown in FIG. 3 will be mainly described.
- the present invention is applicable to various solar cell modules such as a crystalline silicon solar cell module using a crystalline silicon substrate. Is also applicable.
- the transparent insulating substrate 1 a glass plate, a plate member made of a transparent resin, a sheet member, or the like is used.
- a glass plate is preferable because it has high transmittance and is inexpensive.
- the solar battery cell 5 formed on the main surface opposite to the surface on which the antiglare film 50 is formed on the transparent insulating substrate 1 is not particularly limited.
- a crystalline silicon solar cell using a single crystal silicon substrate or a polycrystalline silicon substrate. Examples include batteries, silicon-based thin film solar cells using amorphous silicon thin films, crystalline silicon thin films, and the like, compound solar cells such as CIGS and CIS, organic thin film solar cells, and dye-sensitized solar cells.
- a first electrode layer 2 a photoelectric conversion unit 3, and a second electrode layer 4 are sequentially formed on a transparent insulating substrate 1.
- a transparent conductive metal oxide such as ITO, SnO 2 , or ZnO is preferably used.
- silicon-based semiconductor thin films such as amorphous silicon, amorphous silicon carbide, amorphous silicon germanium, and crystalline silicon are combined in a pin type, nip type, ni type, pn type, and the like.
- a semiconductor junction is used.
- the photoelectric conversion unit 3 may be a tandem type having a plurality of pn junctions, pin junctions, and the like.
- a reflective metal layer such as Ag or Al, a composite layer of a metal layer and a conductive metal oxide layer, or the like is used.
- a solar cell module includes a plurality of solar cells, and each solar cell is electrically connected in series or in parallel.
- a linear separation groove is provided in each layer of the first electrode layer 2, the photoelectric conversion unit 3, and the second electrode layer 4, and a plurality of cells are formed by dividing each layer into a plurality of regions.
- Each cell is preferably electrically connected.
- FIG. 3 shows a configuration in which three photoelectric conversion cells are connected in series.
- an integrated solar cell in which each layer is divided into a plurality of cells by separation grooves can be formed by sequentially repeating the formation of each layer and the formation of separation grooves by patterning means such as laser scribing.
- the integrated solar cell 5 shown in FIG. 3 is manufactured by the following process.
- the photoelectric conversion unit 3 is formed on the first electrode layer 2. Thereafter, a separation groove is formed in the photoelectric conversion unit 3 and divided into predetermined patterns by laser scribing with a laser incident from the transparent insulating substrate 1 side. Thereafter, a second electrode layer is formed on the photoelectric conversion unit 3, and a separation groove is formed by blowing off the second electrode layer 4 together with the photoelectric conversion unit 3 by laser scribing with a laser incident from the transparent insulating substrate 1 side.
- the formation of the antiglare film 50 on the transparent insulating substrate 1 is preferably performed after laser scribing.
- the filling resin 6 and the back surface sealing board 7 are provided.
- the filling resin 6 silicon, ethylene vinyl acetate, polyvinyl butyral or the like is used, and as the back surface sealing plate, a fluorine resin film, a polyethylene terephthalate film, a metal film such as aluminum, a laminate thereof, or A film having a multilayer structure in which a thin film such as SiO 2 is laminated on these films is used.
- An antiglare film 50 is formed on the surface of the transparent insulating substrate 1 opposite to the surface on which the solar cells 5 are formed.
- the antiglare film can be formed either before or after the formation of the solar battery cell 5 on the transparent insulating substrate 1.
- the antiglare film 50 is formed after the solar battery cells 5 are formed and integrated by laser scribing.
- the antiglare film can be formed at any time after laser scribing, and may be immediately after scribing, after sealing with the filling resin 6 and the back surface sealing plate 7, or after the module is installed on the roof or wall surface. .
- the solar cell module before the anti-glare film is formed on the substrate surface is outdoors (for example, in the premises of the housing where the module is installed).
- An anti-glare film can also be formed after moving to, and before installing on a roof etc. According to such a method, for example, an antiglare film is selectively formed only on a solar cell module installed in an orientation opposite to the solar radiation surface (for example, the north side in the case of the northern hemisphere) to prevent light pollution. Etc. are also possible.
- the antiglare film 50 may be formed on the entire surface of the transparent insulating substrate 1 or may be formed on only a part thereof. For example, an anti-glare region where an anti-glare film is formed on the transparent insulating substrate 1 and a non-glare region where no anti-glare film is formed can be formed.
- a pattern anti-glare film may be formed by forming the anti-glare region and the non-glare region into a predetermined pattern shape. For example, before forming the anti-glare film, a mask material such as a water-resistant tape is attached to a part of the surface of the transparent insulating substrate 1 to cover the substrate surface, and selectively anti-glare to an area where no mask is attached.
- a solar cell module with a pattern antiglare film as shown in FIG. 5 may be formed.
- the character portion is formed as a non-glare-proof region by forming an anti-glare film after the character portion is covered with a mask material.
- the character portion is made an anti-glare region by forming an anti-glare film after covering the portion other than the character with a mask material.
- the shape of the anti-glare region or the non-glare region is not particularly limited, and may be a mark, a pattern, a pattern, or the like in addition to characters.
- Example 1 (Preparation of coating solution)
- a coating liquid for forming the first inorganic layer (first coating liquid)
- a polysilazane-containing solution (trade name manufactured by AZ Electromaterial Co., Ltd. containing perhydropolysilazane having a solid concentration of 20% by weight in dibutyl ether: “ Aquamica NAX120-20 ”)
- 2.5 parts by weight of silica beads (manufactured by Admatechs Co., Ltd., average primary particle size: 1.2 ⁇ m) is added to 20 parts by weight
- 77.5 parts by weight of dibutyl ether is added as a solvent.
- This coating solution contained 62.5 parts by weight of fine particles with respect to 100 parts by weight of polysilazane, and the total solid concentration was 6.5% by weight.
- a coating solution for forming the second inorganic layer As a coating solution for forming the second inorganic layer (second coating solution), a coating solution was prepared by adding 80 parts by weight of dibutyl ether as a solvent to 20 parts by weight of a polysilazane-containing solution (AQUAMICA NAX120-20). . The solid content concentration of this coating solution was 4.0% by weight.
- a transparent glass substrate having a thickness of 3.2 mm and a size of 1400 mm ⁇ 1100 mm was washed with tap water, and then water droplets were blown off with an air knife, followed by drying.
- Said 1st coating liquid was apply
- the second coating solution was applied by a spray method so that the film thickness after drying was about 300 nm. .
- the two-layer coating film was dried at room temperature and then allowed to stand for 24 hours to cure the binder, thereby obtaining an antiglare film mainly composed of silicon oxide.
- Microscopic infrared spectroscopy infrared was measured with the spectrum, around 1060 cm -1 derived from Si-O bond antiglare film binder portion after standing this 24-hour period (a portion other than the fine particles), around 800 cm -1 and in addition to the peak near 450 cm -1, 2160 cm -1 vicinity (Si-H bonds), 840 cm -1 vicinity (Si-N bonds), and a peak was observed at 3370cm around -1 (N-H bonds).
- the glass substrate on which the antiglare film was formed was left in the outdoor environment for 2 months, and the infrared spectrum was measured again. As a result, the peaks near 2160 cm ⁇ 1 , 840 cm ⁇ 1 , and 3370 cm ⁇ 1 disappeared. It was confirmed that Si—O bonds were generated by hydrolysis of Si—H bonds and Si—N bonds.
- Example 2 an antiglare film containing fine particles was formed in the second inorganic layer.
- a polysilazane-containing solution (Aquamica NAX120-20) was added to a dispersion of hollow colloidal silica (colloidal silica having a solid content concentration of 20% by weight in methyl isobutyl ketone (average secondary particle size 50 nm)).
- 20 parts by weight of a dispersion liquid containing 40 parts by weight of dibutyl ether as a solvent was added to prepare a coating solution.
- This coating solution contained 100 parts by weight of fine particles with respect to 100 parts by weight of the solid content of polysilazane, and the total solid content concentration was 8.0% by weight.
- the average film thickness d 1 is determined by the spray method in the same manner as in Example 1 except that the above-mentioned coating liquid containing colloidal silica is used as the second coating liquid for forming the second inorganic layer.
- a first inorganic layer of about 1000 nm, antiglare film comprising a second inorganic layer containing colloidal silica particles in the film with an average thickness d 2 of about 300nm is formed.
- Example 1 A first coating solution similar to that in Example 1 was applied on a glass substrate by a spray method, and then the second coating solution was not sprayed to form an antiglare film consisting only of the first inorganic layer.
- Example 2 In preparation of the first coating solution, 1.5 parts by weight of crushed glass powder (manufactured by Nippon Frit Co., Ltd., average secondary particle size: 1.0 ⁇ m) was added instead of silica beads. Otherwise in the same manner as in Example 1, by spraying, on the first inorganic layer having an average thickness d 1 of about 1000 nm, antiglare average thickness d 2 comprises a second inorganic layer of about 300nm A film was formed.
- crushed glass powder manufactured by Nippon Frit Co., Ltd., average secondary particle size: 1.0 ⁇ m
- Comparative Example 3 A first coating solution similar to that in Comparative Example 2 was applied on a glass substrate by a spray method, and then the second coating solution was not sprayed, and an antiglare film consisting only of the first inorganic layer was formed.
- the anti-glare film of Comparative Example 2 remained unremoved even after 20 reciprocations (same as the case of 5 reciprocations of Comparative Example 1), and the pencil line was almost wiped off after approximately 200 reciprocations.
- the antiglare film of Comparative Example 3 remained undissolved even after 200 reciprocations.
- the photograph at the time of 5 reciprocating wiping of the anti-glare film of Example 2 and Comparative Example 1 is shown in FIG. In each photograph of FIG. 9, the left side (a) of the glass plate is before wiping, and the right side (b) of the glass plate is after wiping five times.
- Table 1 shows the evaluation results of the antiglare films obtained in the above Examples and Comparative Examples together with the composition of the coating solution used in each Example.
- the SEM observation image of the surface and the cross section of the antiglare film of Example 2 is shown in FIG. 6
- the SEM observation image of the surface and the cross section of the antiglare film of Comparative Example 1 is shown in FIG.
- the SEM observation images of the surface and the cross section are shown in FIG.
- (b) is an enlarged observation image of the frame-enclosed portion in (a)
- (d) is an enlarged observation image of the frame-enclosed portion in (c).
- the antiglare film of the present invention has a concavo-convex pattern of fine particles in the first layer. It can be seen that the concave portion of the first inorganic layer is filled with the second inorganic layer while maintaining the above. As described above, in the present invention, the formation of the second inorganic layer on the first inorganic layer suppresses the entry of contaminants deep into the concave portion, and the dirt wiping property is improved. Conceivable.
- ⁇ Evaluation of conversion characteristics> 3 is formed by sequentially forming a transparent electrode layer, a laminated photoelectric conversion unit comprising a pin junction amorphous silicon photoelectric conversion unit and a pin junction crystalline silicon photoelectric conversion unit, and a metal back electrode on a glass substrate.
- Type thin film solar cell module (however, it does not have the anti-glare film 50 and the frame 8 is not installed) was produced. A total of 20 similar modules were produced, and the output characteristics of each module were measured using a solar simulator.
- an antiglare film was formed on the surface of the glass substrate opposite to the cell formation surface by the same method as in Example 2 to obtain a solar cell module with an antiglare film.
- Comparison of conversion characteristics before and after antiglare film formation of each module revealed that short circuit current density (Isc) increased by 1.5% to 2.1% (average 1.8%) after the antiglare film was formed.
- the voltage (Voc) increased by 0.1% to 0.3% (average 0.2%), and the maximum output increased by 2.0% to 2.5% (average 2.2%).
- the anti-glare film of the present invention has a two-layer structure including the second inorganic layer on the first inorganic layer, the removability of contaminants is improved and the anti-glare film in the second inorganic layer It can be seen that the antireflective effect is enhanced by adding low refractive index fine particles to the glass, which also contributes to an improvement in conversion efficiency due to an increase in the amount of light taken into the solar cell module.
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Abstract
Description
図1は、本発明による一実施形態の太陽電池モジュール用防眩膜の概略構成を示す断面図であり、透明絶縁基板1上に、防眩膜50が形成されている。
第一の無機層10は、無機バインダ11中に透明な無機微粒子12を含有する。
第一の無機層の無機バインダ11としては、シリコン酸化物が好適に用いられ、中でも、Si-H結合およびSi-N結合の加水分解によって得られるSi-O結合を含有するシリコン酸化物が好適に用いられる。シリコン酸化物が、Si-H結合やSi-N結合の加水分解によるSi-O結合を含有する場合、バインダの透明性が高いことに加えて、ガラス等の透明絶縁基板との密着性や、耐光性、硬度等に優れる。
第一の無機層10に含まれる無機微粒子12としては、球状の微粒子が好ましく用いられる。粒子が球状の場合、膜表面の凸部が曲面形状となり、凹凸の起伏がなだらかとなるため、砂埃や花粉等の汚染物質の防眩膜表面の凹凸構造への入り込みが抑制される。なお、「球状」の微粒子は、必ずしも真球である必要はなく、表面が曲面状であれば扁平状等でもよい。
第一の無機層10の平均膜厚d1は、500nm~2000nmが好ましく、750nm~1750nmがより好ましく、1000nm~1500nmがさらに好ましい。膜厚d1が500nm以上であれば、一次平均粒径が100nmを超える無機微粒子12を基板表面に強固に付着することができる。また、膜厚d1が2000nm以下であれば、第一の無機層10の表面に、微粒子12の形状に倣った凹凸が形成され、これに倣った凹凸パターンが防眩膜50表面に形成されるため、防眩性が高められる。第一の無機層10が塗布法により形成される場合、平均膜厚d1は、塗布液の固形分濃度、塗布量および塗布面積から算出することができる。
透明絶縁基板1上に第一の無機層10を形成する方法は特に制限されないが、シリコン酸化物バインダあるいはその前駆体、および微粒子を含有する溶液を、透明絶縁基板1上に塗布する方法が適している。塗布方法としては、ディッピング法、スピンコート法、バーコート法、ダイコート法、ロールコート法(印刷法)、フローコート法、スプレー法等が挙げられる。これらの塗布法のうち、スプレー法は特別な設備を必要とせず、セルの封止後や、モジュールを屋根等に設置した後でも、絶縁基板上に防眩膜を容易に形成できるため好ましい。
第一の無機層10上には、第二の無機層20が形成される。第二の無機層20は、バインダ21を含有する。
第二の無機層20を構成するバインダ21は、第一の無機層10との密着性に優れる材料が好ましく、無機バインダが好適に用いられる。無機バインダ21は、透明性を有するものであれば、特に限定されないが、シリコン系化合物が好適に用いられる。シリコン系化合物の具体例としては、テトラメチルシリケート、テトラエチルシリケート、テトラ-n-プロピルシリケート、テトラ-i-プロピルシリケート、テトラ-n-ブチルシリケート、テトラ-i-ブチルシリケート、テトラ-t-ブチルシリケート等のテトラアルキルシリケート;メチルトリメトキシシラン、メチルトリエトキシシラン、オクタデシルトリエトキシシラン、メチルトリ-sec-オクチルオキシシラン、メチルトリイソプロポキシシラン、メチルトリブトキシシラン等のアルキルトリアルコキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン等のアリールトリアルコキシシラン、メチルトリフェノキシシラン等のアルキルトリアリールオキシシラン、3-グリシドキシプロピルトリメトキシシラン等のグリシドキシトリアルコキシシラン等のトリアルコキシシランまたはトリアリールオキシシラン等が挙げられる。
第二の無機層20の平均膜厚d2は、50nm~1000nmが好ましく、75nm~750nmがより好ましく、100nm~500nmがさらに好ましい。また、第一の無機層10の平均膜厚d1と第二の無機層20の平均膜厚d2との比率d2/d1は、0.025~0.5が好ましく、0.04~0.4がより好ましく、0.06~0.3がさらに好ましい。
第二の無機層20の平均屈折率n2は、第一の無機層10の平均屈折率n1よりも小さいことが好ましい。n2とn2との差は、0.03以上が好ましく、0.05以上がより好ましく、0.07以上がさらに好ましく、0.10以上が特に好ましい。主に酸化シリコンからなる第一の無機層10の平均屈折率n1が1.45~1.55程度であるのに対して、第二の無機層20の平均屈折率n2は、1.45以下が好ましく、1.40以下がさらに好ましい。
第二の無機層20中に無機微粒子22を含有する場合、防眩膜の断面観察から算出される平均一次粒子径は、10nm~300nmが好ましく、20nm~150nmがより好ましく、30nm~100nmがさらに好ましい。また、第一の無機層10表面の凹凸形状を緩和するとの観点から、第二の無機層20中の無機微粒子22の平均一次粒径は、第一の無機層10中の無機微粒子12の平均一次粒径よりも小さいことが好ましい。
第一の無機層10上に第二の無機層20を形成する方法は特に制限されないが、第一の無機層10の形成と同様に、スプレー法等の塗布法が好ましい。
上記の防眩膜を、太陽電池モジュールの受光面側表面に設けることで、防眩膜付き太陽電池モジュールが形成される。図3は、一実施形態にかかる防眩膜付き薄膜太陽電池モジュールの概略構成を示す断面図である。この太陽電池モジュールは、透明絶縁基板1と、透明絶縁基板1の第一の主面に形成された太陽電池セル5を備え、透光性基板の第二の主面に防眩膜50を備える。
(塗布液の調製)
第一の無機層形成用の塗布液(第一塗布液)として、ポリシラザン含有溶液(ジブチルエーテル中に固形分濃度20重量%のパーヒドロポリシラザンを含有するAZエレクトロマテリアル株式会社製の商品名:「アクアミカ NAX120-20」)20重量部に、シリカビーズ(株式会社アドマテックス製、平均一次粒子径:1.2μm)を2.5重量部添加し、さらに溶媒としてジブチルエーテルを77.5重量部添加して、塗布液を調製した。この塗布液は、ポリシラザン100重量部に対して微粒子を62.5重量部含有し、総固形分濃度は6.5重量%であった。
厚み3.2mm、サイズ1400mm×1100mmの透明ガラス基板を水道水により洗浄した後、エアナイフにて水滴を飛ばし、乾燥を行った。乾燥後のガラス基板の一方の面に、上記の第一塗布液を、乾燥後の膜厚が1.0μmとなるようにスプレー法により塗布した。第一塗布液をスプレー後、約20秒後(塗膜表面が乾燥した状態となった後)に、第二塗布液を、乾燥後の膜厚が300nm程度となるようにスプレー法により塗布した。
実施例2では、第二の無機層中に微粒子を含有する防眩膜が形成された。第二塗布液として、ポリシラザン含有溶液(アクアミカ NAX120-20」)20重量部に、中空コロイダルシリカの分散液(メチルイソブチルケトン中に固形分濃度20重量%のコロイダルシリカ(平均二次粒子径50nm)を含有する分散液)を20重量部添加し、さらに溶媒としてジブチルエーテルを40重量部添加して、塗布液を調製した。この塗布液は、ポリシラザンの固形分100重量部に対して微粒子を100重量部含有し、総固形分濃度は8.0重量%であった。
実施例1と同様の第一塗布液をスプレー法によりガラス基板上に塗布した後、第二塗布液のスプレーを行わず、第一の無機層のみからなる防眩膜を形成した。
第一塗布液の調製において、シリカビーズに代えて、粉砕ガラス粉末(日本フリット株式会社製、平均二次粒子径:1.0μm)を1.5重量部添加した。それ以外は実施例1と同様にして、スプレー法により、平均膜厚d1が約1000nmの第一の無機層上に、平均膜厚d2が約300nmの第二の無機層を備える防眩膜が形成された。
比較例2と同様の第一塗布液をスプレー法によりガラス基板上に塗布した後、第二塗布液のスプレーを行わず、第一の無機層のみからなる防眩膜を形成した。
<防眩性>
防眩膜が形成されたガラス基板に、白色蛍光灯の光を照射し、その反射光を目視観察したところ、いずれの実施例および比較例の防眩膜も、蛍光灯の像がぼやけて見え、防眩性に優れることが確認された。
各実施例および比較例のそれぞれの防眩膜上に、硬度6Bの鉛筆で長さ約5cmの線を3本描き、水道水で湿らせたベンコットを押し当て、一定の押圧で防眩膜上を往復させて水拭きを行い、何往復で鉛筆の汚れが消えるかを確認した。実施例1および実施例2の防眩膜は、いずれも5往復で鉛筆の線が拭き取られた。一方、比較例1の防眩膜は、5往復では消え残りがあり、20往復で鉛筆の線が拭き取られた。比較例2の防眩膜は、20往復でも消え残り(比較例1の5往復の場合と同程度)があり、約200往復で鉛筆の線がほぼ拭き取られた。比較例3の防眩膜は、200往復でも消え残りがあった。実施例2および比較例1の防眩膜の5往復拭き取り時の写真を図9に示す。図9の各写真において、ガラス板の左側(a)は拭き取り前、ガラス板の右側(b)は5回拭き取り後である。
ガラス基板上に、透明電極層、pin接合の非晶質シリコン光電変換ユニットおよびpin接合の結晶質シリコン光電変換ユニットからなる積層光電変換ユニット、および金属裏面電極を順次形成して、図3示す集積型薄膜太陽電池モジュール(ただし、防眩膜50を有さず、フレーム8が設置されていない)を作製した。同様のモジュールを計20個作製し、ソーラーシミュレータを用いて、各モジュールの出力特性を測定した。
11,21 バインダ
12 微粒子(非中空微粒子)
22 微粒子(中空微粒子)
50 防眩膜
1 透明絶縁基板
2,4 電極層
3 光電変換ユニット
5 太陽電池セル
6 充填樹脂
7 裏面封止板
8 フレーム
Claims (26)
- 太陽電池モジュールの透明絶縁基板上に形成して用いられる太陽電池モジュール用防眩膜であって、
基板側から、第一の無機層および第二の無機層をこの順に有し、
前記第一の無機層は、無機バインダ中に透明な球形無機微粒子を含有し、クラックを有していない連続皮膜であり、
前記第一の無機層中の前記無機バインダは、Si-H結合およびSi-N結合の加水分解によって得られる、Si-O結合を含有するシリコン酸化物を主成分とするものであり、
前記第二の無機層は、無機バインダを含有し、
前記第一の無機層の平均膜厚d1が500nm~2000nmであり、前記第二の無機層の平均膜厚d2が50nm~1000nmであり、かつd2/d1が0.025~0.5である、太陽電池モジュール用防眩膜。 - 前記第一の無機層中の前記無機微粒子は、防眩膜の断面観察から算出される平均一次粒子径が0.1μm~5.0μmである、請求項1に記載の防眩膜。
- 第二の無機層側表面の最大高さRy2が1.0μm~10μmである、請求項1または2に記載の防眩膜。
- 前記第二の無機層側表面の最大高さRy2が、前記第一の無機層の前記第二の無機層との界面における最大高さRy1よりも小さい、請求項3に記載の防眩膜。
- 前記防眩膜の第二の無機層側表面の算術平均粗さRa2が0.25μm~2μmであり、かつ凹凸周期Sm2が1μm~30μmである、請求項1~4のいずれか1項に記載の防眩膜。
- 防眩膜の合計平均膜厚dと、防眩膜の第二の無機層側表面の最大高さRy2との比Ry2/dが1~20である、請求項1~5のいずれか1項に記載の防眩膜。
- 前記第二の無機層の平均屈折率n2が、前記第一の無機層の平均屈折率n1よりも小さい、請求項1~6のいずれか1項に記載の防眩膜。
- 前記第二の無機層は、前記第二の無機層中の前記バインダよりも低屈折率の無機微粒子をさらに含有する、請求項7に記載の防眩膜。
- 前記第二の無機層中の前記無機微粒子は、防眩膜の断面観察から算出される平均一次粒子径が10nm~300nmであり、かつ前記第一の無機層中の前記無機微粒子よりも平均一次粒子径が小さい、請求項8に記載の防眩膜。
- 前記第二の無機層中の前記無機微粒子が中空微粒子である、請求項8または9に記載の防眩膜。
- 前記第二の無機層中の前記無機微粒子が中空コロイダルシリカである、請求項10に記載の防眩膜。
- 前記第二の無機層中の前記無機バインダは、Si-H結合およびSi-N結合の加水分解によって得られる、Si-O結合を含有するシリコン酸化物を主成分とするものである、請求項1~11のいずれか1項に記載の防眩膜。
- 前記第一の無機層中の前記無機微粒子は、SiO2を主成分とするものである、請求項1~12のいずれか1項に記載の防眩膜。
- 前記第一の無機層中に、顔料または染料をさらに含有する請求項1~13のいずれか1項に記載の防眩膜。
- 透明絶縁基板の第一の主面に少なくとも1つの太陽電池セルを備え、前記透明絶縁基板の第二の主面に請求項1~14のいずれか1項に記載の防眩膜を備える、太陽電池モジュール。
- 前記少なくとも1つの太陽電池セルは、前記透明絶縁基板側から第一電極層、光電変換ユニットおよび第二電極層を備え、これらの各層に線状の分離溝が設けられることにより複数のセルに分割されるとともに、複数のセルが電気的に直列または並列に接続されている、請求項15に記載の太陽電池モジュール。
- 前記少なくとも1つの太陽電池セルは、結晶シリコン基板を備える結晶シリコン系太陽電池セルである、請求項15に記載の太陽電池モジュール。
- 前記透明絶縁基板の第二の主面上に、前記防眩膜が形成された防眩領域と、防眩膜が形成されていない非防眩領域とを有する、請求項15~17のいずれか1項に記載の太陽電池モジュール。
- 請求項1~14のいずれか1項に記載の防眩膜を形成する方法であって、
透明絶縁基板の一方の主面に、第一の塗布液が塗布される第一塗布工程;
前記第一の塗布液の塗布膜上に、第二の塗布液が塗布される第二塗布工程;および
前記第一の塗布液および前記第二の塗布液中の溶媒が乾燥され塗布膜が硬化される硬化工程、を有し、
前記第一の塗布液は、透明な球形無機微粒子0.01~20重量%、ポリシラザン0.1~20重量%および溶媒を含有し、前記無機微粒子の平均一次粒子径が0.1μm~5.0μmである、防眩膜の形成方法。 - 前記第二の塗布液は、ポリシラザン0.1~20重量%および溶媒を含有する、請求項19に記載の防眩膜の形成方法。
- 前記第二の塗布液は、平均一次粒子径が10nm~300nmの無機微粒子0.01~20重量%をさらに含有する、請求項20に記載の防眩膜の形成方法。
- 前記第一塗布工程および前記第二塗布工程が、いずれもスプレー法により行われる、請求項19~21のいずれか1項に記載の防眩膜の形成方法。
- 請求項15~18のいずれか1項に記載の太陽電池モジュールを製造する方法であって、
前記透明絶縁基板の第一の主面に太陽電池セルが形成されるセル形成工程後に、前記透明絶縁基板の第二の主面に防眩膜が形成される防眩膜形成工程が実施される、太陽電池モジュールの製造方法。 - 前記セル形成工程が屋内で行われた後、セル形成後の基板が屋外に搬出され、前記防眩膜形成工程が屋外で行われ、
前記透明絶縁基板の第二の主面上への前記防眩膜の形成がスプレー法によって行われる、請求項23に記載の太陽電池モジュールの製造方法。 - 請求項16に記載の太陽電池モジュールを製造する方法であって、
前記透明絶縁基板の第一の主面に太陽電池セルが形成されるセル形成工程後に、前記透明絶縁基板の第二の主面に防眩膜が形成される防眩膜形成工程が実施され、
前記セル形成工程において、前記透明絶縁基板の第二の主面側からレーザ光が照射されることにより、前記分離溝が形成される、太陽電池モジュールの製造方法。 - 請求項18に記載の太陽電池モジュールを製造する方法であって、
前記透明絶縁基板の表面の一部にマスク材が付設される被覆工程が行われた後、
前記透明絶縁基板の表面のマスクが付設されていない領域に前記防眩膜が形成される、太陽電池モジュールの製造方法。
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