CN107073520A - Aqueous coating fluid, film and its manufacture method, layered product and solar module - Google Patents
Aqueous coating fluid, film and its manufacture method, layered product and solar module Download PDFInfo
- Publication number
- CN107073520A CN107073520A CN201580056689.2A CN201580056689A CN107073520A CN 107073520 A CN107073520 A CN 107073520A CN 201580056689 A CN201580056689 A CN 201580056689A CN 107073520 A CN107073520 A CN 107073520A
- Authority
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- China
- Prior art keywords
- film
- aqueous coating
- coating fluid
- particle
- manufacture method
- Prior art date
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- 239000011248 coating agent Substances 0.000 title claims abstract description 141
- 238000000576 coating method Methods 0.000 title claims abstract description 141
- 239000012530 fluid Substances 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 85
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 289
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 143
- 239000011856 silicon-based particle Substances 0.000 claims abstract description 58
- 239000011164 primary particle Substances 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000004094 surface-active agent Substances 0.000 claims abstract description 37
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 34
- 239000008187 granular material Substances 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 31
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 35
- 238000010304 firing Methods 0.000 claims description 17
- 230000000149 penetrating effect Effects 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 159
- 239000012528 membrane Substances 0.000 description 59
- 239000006185 dispersion Substances 0.000 description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 239000002689 soil Substances 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- 239000000470 constituent Substances 0.000 description 17
- 239000011521 glass Substances 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 230000003746 surface roughness Effects 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000011324 bead Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002563 ionic surfactant Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000002310 reflectometry Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 6
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000012736 aqueous medium Substances 0.000 description 5
- 239000008199 coating composition Substances 0.000 description 5
- 230000001976 improved effect Effects 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000010422 painting Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229920013800 TRITON BG-10 Polymers 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- -1 which is included Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910003978 SiClx Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011257 shell material Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 2
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-UHFFFAOYSA-N 0.000 description 1
- HBXWUCXDUUJDRB-UHFFFAOYSA-N 1-octadecoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCCCC HBXWUCXDUUJDRB-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 244000050510 Cunninghamia lanceolata Species 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical class CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 235000019082 Osmanthus Nutrition 0.000 description 1
- 241000333181 Osmanthus Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- RPPBZEBXAAZZJH-UHFFFAOYSA-N cadmium telluride Chemical compound [Te]=[Cd] RPPBZEBXAAZZJH-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical class CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- WQQPDTLGLVLNOH-UHFFFAOYSA-M sodium;4-hydroxy-4-oxo-3-sulfobutanoate Chemical class [Na+].OC(=O)CC(C([O-])=O)S(O)(=O)=O WQQPDTLGLVLNOH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- 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
-
- 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
- H01L31/0216—Coatings
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to a kind of manufacture method of film and its application, the manufacture method of the film includes：The process for being coated with aqueous coating fluid on base material and forming coated film, the aqueous coating fluid is that a kind of below 8nm nonporous silica silicon particle, surfactant, and pH are 1.5~3.5 comprising water, as the average primary particle diameter of silicon dioxide granule；And the process that the coated film for being coated with formation is dried.
Description
Technical field
The present invention relates to a kind of aqueous coating fluid, film and its manufacture method, layered product and solar module.
Background technology
Aqueous coating fluid containing silicon dioxide microparticle uses the solvent comprising water, and the surface of the film formed can be low
And the transparency is excellent, is thus used in various uses.
As its purposes, antireflection film, optical lens, optical filter, various displays can be suitably applied to
Thin film transistor array (TFT) planarization film, anti-condensation film, anti-soil film and surface protection film etc..
Wherein, antireflection film is because that can be used in such as solar module, CCTV camera, lighting apparatus, label
Diaphragm and it is useful.Various coating compositions and painting method are developed in the purposes of antireflection film.
For example in Japanese Unexamined Patent Application Publication 2013-527879 publications, assigned as to base material in antireflection and durability
The painting method of at least one characteristic, discloses the method for modifying of the substrate surface including following process：Should by coating composition
For the process of base material, the coating composition is comprising non-spherical nano-particle, spherical nano-particle and is arbitrarily lived comprising surface
At least a portion in property agent and water, and non-spherical nano-particle or spherical nano-particle has functional group on surface；And dry
Coating composition and on base material formed hydrophilic coating process.
Also, in No. 5266549 publications of Japanese Patent No., as can be used in the optics such as antireflection coated coating in
Coating composition, disclose comprising the nuclear material containing cation property copolymer and the shell material containing metal oxide, and
Include the composition for the nano-particle that average specific dimensions are more than 10nm and below 200nm.
Also, in Japanese Unexamined Patent Publication 2009-54352 publications, as low-reflection film formation coating, disclose by containing
There is the painting of metal oxide and resin including the silicon dioxide microparticle with air layer and/or porous silica silicon particle
Material.
The content of the invention
The invention technical task to be solved
However, the substrate surface being modified by method described in Japanese Unexamined Patent Application Publication 2013-527879 publications, prevents
Reflectivity is excellent, but can not obtain sufficient marresistance.
Also, the described group in No. 5266549 publications of Japanese Patent No. and Japanese Unexamined Patent Publication 2009-54352 publications
Similarly, antireflection is excellent for the layer that compound or coating are obtained, but marresistance is insufficient.
That is, under actual conditions, the film of antireflection and excellent scratch resistance can not up to be provided.
One embodiment of the present invention is to complete in view of the foregoing, its object is to provide to be formed antireflection and
The aqueous coating fluid of the film of excellent scratch resistance, the film and its manufacture method of antireflection and excellent scratch resistance, layered product and
Solar module, will realize that the purpose is used as problem.
Means for solving technical task
For realizing that the specific mode of problem includes in the following manner.
A kind of manufacture methods of film of the ＞ of ＜ 1, it includes：Aqueous coating fluid is coated with base material and forms the work of coated film
Sequence, a kind of non-porous dioxy that the aqueous coating fluid is below 8nm comprising water, as the average primary particle diameter of silicon dioxide granule
SiClx particle, surfactant, and pH is 1.5~3.5；And the process that the coated film for being coated with formation is dried.
The manufacture method of films of the ＞ of ＜ 2 according to the ＞ of ＜ 1, the average primary particle diameter of nonporous silica silicon particle is 6nm
Below.
The manufacture method of films of the ＞ of ＜ 3 according to the ＞ of ＜ 1 or the ＞ of ＜ 2, the pH of aqueous coating fluid is 1.8~3.0.
The manufacture method of films of the ＞ of ＜ 4 according to any of ＞ of 1 ＞ of ＜~＜ 3, drying coating film process it
Afterwards, in addition to by dried coated film the process burnt till with the temperature of more than 400 DEG C and less than 800 DEG C.
The manufacture method of films of the ＞ of ＜ 5 according to the ＞ of ＜ 4, firing process is more than 500 DEG C and less than 800 DEG C of temperature
It is lower to be burnt till.
The manufacture method of films of the ＞ of ＜ 6 according to the ＞ of ＜ 4 or the ＞ of ＜ 5, firing process is formed and is linked with by burning till
The particle union body of multiple nonporous silica silicon particles.
The manufacture method of films of the ＞ of ＜ 7 according to any of ＞ of 4 ＞ of ＜~＜ 6, the thickness of the coated film after burning till
For more than 50nm and below 350nm.
In the manufacture method of films of the ＞ of ＜ 8 according to any of ＞ of 1 ＞ of ＜~＜ 7, at least dried coated film,
By the light in 400nm~1100nm wavelength that following formula (1) is defined with the absolute value of average reflectance changes delta R during 5 ° of incidence
For more than 2.0%.
| average reflectance changes delta R |=| R1-R2| formula (1)
In formula (1), R1Represent film formed after base material average reflectance, R2Represent the average reflectance of base material.
The manufacture method of films of the ＞ of ＜ 9 according to the ＞ of ＜ 8, average reflectance changes delta R absolute value for 2.5% with
On.
A kind of aqueous coating fluids of the ＞ of ＜ 10, are below 8nm's comprising water, as the average primary particle diameter of silicon dioxide granule
A kind of nonporous silica silicon particle, surfactant, and pH is 1.5~3.5.
Aqueous coating fluids of the ＞ of ＜ 11 according to the ＞ of ＜ 10, the average primary particle diameter of nonporous silica silicon particle is 6nm
Below.
Aqueous coating fluids of the ＞ of ＜ 12 according to the ＞ of ＜ 10 or the ＞ of ＜ 11, the pH of aqueous coating fluid is 1.8~3.0.
Aqueous coating fluid described in any one of the ＞ of ＜ 13 in the ＞ of 10 ＞ of ＜~＜ 12, surfactant is nonionic
Type surfactant.
A kind of films of the ＞ of ＜ 14, are a kind of non-porous the two of below 8nm containing the average primary particle diameter as silicon dioxide granule
Silicon oxide particle, and thickness is more than 50nm and below 350nm.
Films of the ＞ of ＜ 15 according to the ＞ of ＜ 14, the average primary particle diameter of nonporous silica silicon particle is below 6nm.
Films of the ＞ of ＜ 16 according to the ＞ of ＜ 14 or the ＞ of ＜ 15, by following formula (1) define in 400nm~1100nm wavelength
Light using the absolute value of average reflectance changes delta R during 5 ° of incidence as more than 2.0%.
| average reflectance changes delta R |=| R1-R2| formula (1)
In formula (1), R1Represent film formed after base material average reflectance, R2Represent the average reflectance of base material.
Films of the ＞ of ＜ 17 according to the ＞ of ＜ 16, average reflectance changes delta R absolute value is more than 2.5%.
Films of the ＞ of ＜ 18 according to any of ＞ of 14 ＞ of ＜~＜ 17, to be linked with multiple nonporous silica silicon particles
The state of particle union body contain nonporous silica silicon particle.
Films of the ＞ of ＜ 19 according to any of ＞ of 14 ＞ of ＜~＜ 17, also contains surfactant.
Films of the ＞ of ＜ 20 according to any of ＞ of 14 ＞ of ＜~＜ 19, surface roughness Ra is below 20nm.
A kind of layered products of the ＞ of ＜ 21, on base material, with passing through the manufacture method described in any of ＞ of 1 ＞ of ＜~＜ 9
And the film manufactured, or pass through the film described in any of ＞ of 14 ＞ of ＜~＜ 20.
Layered products of the ＞ of ＜ 22 according to the ＞ of ＜ 21, base material is glass baseplate.
A kind of solar modules of the ＞ of ＜ 23, possess the layered product described in the ＞ of the ＜ 21 or ＞ of ＜ 22.
Invention effect
The aqueous coating for the film for forming antireflection and excellent scratch resistance is provided according to an embodiment of the present invention
Film and its manufacture method, the layered product and solar module of liquid, antireflection and excellent scratch resistance.
Embodiment
The manufacture method ＞ of ＜ films
The manufacture method of film includes：The process for being coated with aqueous coating fluid on base material and forming coated film, the aqueous painting
Cloth liquid is a kind of below 8nm nonporous silica silicon particle, surface comprising water, as the average primary particle diameter of silicon dioxide granule
Activating agent, and pH is 1.5~3.5；And the process that the coated film for being coated with formation is dried.
The manufacture method of film preferably also includes dried coated film with 400 DEG C after the process of drying coating film
Above and the process burnt till of less than 800 DEG C of temperature.
Although the effect of one embodiment of the present invention is simultaneously indefinite, presumption can be carried out as follows.
The manufacture method of the film of one embodiment of the present invention, silica is used as in aqueous coating solution comprising one kind
The average primary particle diameter of particle is below 8nm nonporous silica silicon particle, the pH of aqueous coating fluid is controlled, so that non-porous dioxy
The Zeta potential value of SiClx particle surface turns into zero or (pH of aqueous coating fluid is set to close to zero close to silica
The isoelectric point of particle is pH2.0 value), thus, nonporous silica silicon particle is when forming the film for forming weak state of aggregation
Higher pore volume can be realized, it is believed that even if without using beads shape (chain) silicon dioxide granule, antireflection can also be formed
The excellent film of property.
Moreover, the average primary particle diameter of nonporous silica silicon particle is below 8nm, it is taken as that the film that is formed it is fine and close and
The excellent scratch resistance of film.
Think these to be combined and can be formed by the silica linked comprising chain, porous silica or hollow
The aqueous coating agent of silica etc. and can not realize, the film of antireflection and excellent scratch resistance.
In addition, the average primary particle diameter of nonporous silica silicon particle is below 8nm, therefore the surface of the film formed is put down
It is sliding, and suppression dirt is attached to film.Therefore the film manufactured by the manufacture method of one embodiment of the present invention, it is not only above-mentioned
Antireflection and excellent scratch resistance, and soil resistance is also excellent.
Hereinafter, on each operation in the manufacture method of the film of one embodiment of the present invention, it will be described in detail.
[process for forming coated film]
The manufacture method of film is included in the process on base material being coated with aqueous coating fluid and form coated film, the aqueous coating
Liquid is a kind of below 8nm nonporous silica silicon particle, surface work comprising water, as the average primary particle diameter of silicon dioxide granule
Property agent, and pH be 1.5~3.5.
(aqueous coating fluid)
Aqueous coating fluid is a kind of non-porous the two of below 8nm comprising water, as the average primary particle diameter of silicon dioxide granule
Silicon oxide particle, surfactant, and pH is 1.5~3.5.
Aqueous coating fluid includes the nonporous silica that a kind of average primary particle diameter as silicon dioxide granule is below 8nm
Silicon particle, this is even more important in terms of antireflection.That is, it was not to use these silicon dioxide granules in the past, but used specific
The nonporous silica silicon particle of average primary particle diameter formed using beads shape (chain) silicon dioxide granule or porous dioxy
The film of SiClx particle, thus, the marresistance that can not be met with beads shape silicon dioxide granule can be maintained well on the contrary, and
Antireflection can be assigned.Moreover, being combined with the pH of aqueous coating fluid for 1.5~3.5, the improvement of antireflection can be improved
Effect.
Also, due to being below 8nm very fine silicon dioxide granule using average primary particle diameter, therefore formed
Coated film it is fine and close and surface is smooth, therefore marresistance and soil resistance are excellent.
From the point of view, in aqueous coating fluid, the average primary particle diameter of nonporous silica silicon particle is preferably 6nm
Hereinafter, and pH be 1.8~3.0.
- nonporous silica silicon particle-
A kind of nonporous silica that it is below 8nm as the average primary particle diameter of silicon dioxide granule that aqueous coating fluid, which is included,
Silicon particle.
" nonporous silica silicon particle " refers to the particle for not having space in the inside of silicon dioxide granule, is different from
There is the particle in space inside empty silicon dioxide granule and porous silica silicon particle etc..Also, " nonporous silica silicon particle "
In do not include the silicon dioxide granule of following nucleocapsid structure：There is the cores such as polymer in the inside of particle, the shell (shell) of core by
The precursor (such as the raw material by burning till and becoming silica) of silica or silica is constituted.
The average primary particle diameter of nonporous silica silicon particle is below 8nm.If average primary particle diameter is more than 8nm, counnter attack
Penetrating property is poor.
Consider that average primary particle diameter is preferably below 6nm, more preferably 2nm~4nm from above-mentioned viewpoint.
Scattered particle is observed by transmission electron microscope, and nonporous silica can be obtained by resulting photo
The average primary particle diameter of silicon particle.The projected area of particle is obtained by the image of photo, is obtained with face equal with projected area
Long-pending diameter of a circle (diameter of equivalent circle), and it is set to average grain diameter (average primary particle diameter).Average once grain in this specification
Footpath uses following value, i.e. on the particle assay projected area of more than 300, diameter of equivalent circle is obtained respectively, and equivalent is justified into straight
The value in footpath carries out the value of arithmetic average.
Nonporous silica silicon particle can use commercially available nonporous silica silicon particle, and for example, NALCO companies
The NALCO (registration mark) 8699,2326,1115 of manufacture.
Content of the nonporous silica silicon particle in aqueous coating solution is excellent relative to the total solid content of aqueous coating fluid
Elect the mass % of 5 mass %~99 as, the matter of more preferably 10 mass %~98 mass %, more preferably 15 mass %~97
Measure %.
Due to nonporous silica silicon particle content within the above range, therefore antireflection, the anti-scratch of aqueous coating fluid
Wound property and soil resistance are excellent, and then, it can be formed with hydrophilic film.
- water-
Aqueous coating fluid contains water.
It is used as the aqueous medium of aqueous coating fluid using water, thus with a large amount of coating fluids using volatile organic solvent
Compare, can significantly mitigate the load to environment.
Aqueous coating fluid can also include hydrophilic organic solvent excellent with the compatibility of water etc..
Aqueous coating fluid includes hydrophilic organic solvent, and thus the surface tension of aqueous coating fluid is further reduced, can be with
Carry out coating evenly.Also, hydrophilic organic solvent be low boiling point organic solvent in the case of, aqueous medium it is low
The ratio of boiling point organic solvent is uprised, therefore has the advantages that easily to dry aqueous coating fluid.
It is without particular limitation as hydrophilic organic solvent, methanol, ethanol, isopropanol, butanol, acetone, second can be enumerated
Glycol and ethyl cellosolve etc..From the viewpoint of easy availability, the reduction of carrying capacity of environment, preferably alcohol, more preferably ethanol
And isopropanol.
It is aqueous to apply in the case that aqueous coating fluid is also used as aqueous medium comprising hydrophilic organic solvent in addition to water
The content of water used in cloth liquid is preferably more than 30 mass % more preferably 40 matter relative to the gross mass of aqueous medium
Measure more than %.
Relative to aqueous coating fluid gross mass solid constituent amount preferably in the mass % of 0.1 mass %~30 scope,
The mass % of more preferably 0.2 mass %~20 scope, the mass % of more preferably 0.5 mass %~10 scope.It is aqueous
The solid constituent amount of coating fluid by adjust aqueous medium content, especially the content of water and can be adjusted.
- surfactant-
Aqueous coating fluid includes at least one surfactant.
Aqueous coating fluid includes surfactant, and thus the coating of aqueous coating fluid is improved, and the table of aqueous coating fluid
Face tension force reduction, therefore uniform applicability, the coated surface state excellent performance of the film formed.
As surfactant, can enumerate nonionic surface active agent, as ionic surfactant it is cloudy from
Subtype surfactant, cationic surface active agent and amphoteric surfactant etc., can be suitably used.
If in addition, ionic surfactant is excessively used, being difficult the pH of aqueous coating fluid being adjusted to defined model
Enclose.Therefore, from the aspect of the free degree of surface-active contents is higher, as surfactant, nonionic is preferably used
Type surfactant.
As the example of nonionic surface active agent, pol yalkylene glycol monoalkyl ether, polyalkylene two can be enumerated
Alcohol monoalkyl ester and polyalkylene glycol mono Arrcostab/monoalky lether etc..As nonionic surface active agent, specifically,
Polyethyleneglycol lauryl ether, polyethyleneglycol stearyl ether, polyethyleneglycol cetyl ether, polyethyleneglycol month can be enumerated
Osmanthus base ester and polyethyleneglycol stearyl etc..
Nonionic surface active agent can use commercially available nonionic surface active agent without special restriction, can be with
Enumerate such as the TRITON BG10 that The Dow Chemical Company are manufactured.
On the other hand, aqueous coating fluid contains ionic surfactant, is thus preferred improving hydrophilic aspect
's.
If aqueous coating fluid excessively contains ionic surfactant, silicon dioxide granule becomes easy cohesion, therefore
It is generally and less with the example of ionic surfactant and silicon dioxide granule.However, adding by ionic surfactant
In the case of being added to aqueous coating fluid, used with the content fewer than the amount for causing silicon dioxide granule to condense, therefore, it is possible to
Improve the soil resistance of the coated film formed by aqueous coating fluid.
As the example of ionic surfactant, alkyl sulfate, alkylbenzenesulfonate and alkyl phosphoric acid can be enumerated
The cationic surface active agents such as the anionic surfactant such as salt, alkyl trimethyl ammonium salt and dialkyl dimethyl ammonium salt,
The amphoteric surfactantes such as alkyl carboxyl glycine betaine.
From the viewpoint of the soil resistance of coated film, the content of the surfactant in aqueous coating solution is relative to aqueous
The gross mass of coating fluid is preferably more than 0.01 mass %, more preferably more than 0.02 mass %, more preferably 0.03 matter
Measure more than %.
By the way that the content of surfactant is set into above range, it is possible to increase wetability, the coating of aqueous coating fluid
Become good.
The upper limit of the content of surfactant is without particular limitation, but because being excessively added according to the species of surfactant and
Surface is segregated to after coating aqueous coating fluid, it is possible to the intensity decreases of coated film.Therefore, surfactant contains
Amount is preferably more preferably below 8 mass % below 10 mass % relative to the gross mass of aqueous coating fluid, more preferably
Below 5 mass %.
Also, in the case of using ionic surfactant as surfactant, from it is further improve soil resistance,
And from the viewpoint of suppression non-porous silicas particle coacervation as caused by the influence of surfactant, ionic surfactant
Content relative to the gross mass of aqueous coating fluid be preferably more preferably below 3.0 mass % below 5.0 mass %, enter one
Step is preferably below 1.0 mass %.
The pH- of-aqueous coating fluid
The pH of aqueous coating fluid is 1.5~3.5.
If the pH of aqueous coating fluid be less than 1.5, antireflection is poor, if also, pH more than 3.5, antireflection is poor.
The reason can be carried out as follows supposition.That is, if the pH of aqueous coating fluid is within the above range, close to average one
Secondary particle diameter is the isoelectric point (pH2.0) of below 8nm nonporous silica silicon particle, therefore nonporous silica silicon particle is in the solution
Weak cohesion is carried out, is applied on base material and is dried in the state of weak cohesion, thus nonporous silica silicon particle is intensive
Ground is configured, and as the film between particle with space.It is thus regarded that film is excellent as antireflection, marresistance and soil resistance
Film.
Consider that the pH of aqueous coating fluid is preferably 1.8~3.0 from above-mentioned viewpoint.In addition, nonporous silica silicon particle etc.
Electricity point shows somewhat dipping and heaving according to manufacture method, primary particle size and surface state, in this case, can coordinate isoelectric point
PH adjust the pH of aqueous coating fluid.
The pH of aqueous coating fluid is to be surveyed using pH instrument (DKK-TOA CORPORATION are manufactured, HM-31P) at 25 DEG C
Fixed value.
(base material)
Without particular limitation to the base material of coating aqueous coating fluid, as base material, glass, resin, metal, ceramics etc. are various
Base material can be suitably used.
In the case of using glass as base material, the condensation of the hydroxyl on the silicon of nonporous silica silicon particle with glass
Also produced between the hydroxyl on surface, be consequently formed the coated film with the excellent adhesion of base material.
As aqueous coating fluid to be coated on to the method for base material without special restriction, for example spraying, brushing, roller coat, rod painting,
Rubbing method can be applicable known to dip-coating etc..
[drying process]
The manufacture method of film includes the process that the coated film for being coated with formation is dried.
By drying coating film, the film comprising nonporous silica silicon particle and surfactant is formed on base material.
The drying of coated film can be carried out under room temperature (25 DEG C), and heater can also be used to carry out.It is used as heating dress
Put, as long as target temperature can be heated to, be then not particularly limited and can use, can for example enumerate baking oven, electric furnace or
Burning apparatus that person coordinates production line and independently made etc..These heaters can be used, by coated film be heated to 40 DEG C~
400 DEG C, so as to be coated the drying of film.Also, in the case where being heated, the heat time can be set to 1 minute~
30 minutes or so.
Drying condition in the process of drying coating film, preferably 40 DEG C~200 DEG C and 1 minute~10 minutes of condition,
More preferably 100 DEG C~180 DEG C and 1 minute~5 minutes of condition.
The dried preferred thickness of coated film is more than 50nm.If thickness is more than 50nm, dried coated film
Antireflection is excellent.
Consider that thickness is preferably more than 50nm and below 350nm, more preferably more than 100nm and 300nm from above-mentioned viewpoint
Hereinafter, more preferably more than 100nm below 250nm.
[firing process]
The manufacture method of film preferably also includes with more than 400 DEG C and less than 800 DEG C after the process of drying coating film
The process that temperature is burnt till to dried coated film.
Nonporous silica silicon particle is before and after firing process, and the state of existing particle changes.Specifically, exist
In coated film before burning till, each nonporous silica silicon particle is used as the single particle (shape condensed by Van der Waals for
The state of the set such as state, in this as single particle) and exist, in the coated film after burning till, multiple nonporous silica silicon grains
At least a portion in son exists with these nonporous silica silicon particles particle union body connected to each other.
In this case, being used by the average primary particle diameter for the particle for burning till and linking, do not consider linking part (for example
Neck portion), and diameter when one in the particle being concatenated only being assumed into spherical.In addition, passing through the grain for burning till and linking
The average primary particle diameter of son can be calculated by the average primary particle diameter identical method with the nonporous silica silicon particle.
In firing process, preferably multiple nonporous silica silicon particles are concatenated by burning till, so as to form particle company
Knot body.Thus, the mutual adhesion of nonporous silica silicon particle is improved, therefore the marresistance of film is further improved.On this
A bit, in the case of based on the aqueous coating fluid for having used the silicon dioxide granule connected in advance with " beads shape ", it is impossible to obtain
Obtain identical effect.
In firing condition in firing process, firing temperature is more preferably more than 450 DEG C and less than 800 DEG C, further excellent
Elect more than 500 DEG C and less than 800 DEG C, especially preferably more than 600 DEG C and less than 800 DEG C as.Also, firing time is preferably 1
Minute~10 minutes, more preferably 1 minute~5 minutes.
Burning till in firing process can use heater to carry out.As heater, as long as mesh can be heated to
Temperature is marked, is just not particularly limited and can use, is independently made for example, electric furnace or cooperation production line
Burning apparatus etc..
The preferred thickness of coated film after burning till is more than 50nm.If thickness is more than 50nm, the coated film after burning till
Antireflection is excellent.
Consider that thickness is preferably more than 50nm and below 350nm, more preferably more than 100nm and 300nm from above-mentioned viewpoint
Hereinafter, more preferably more than 100nm and below 250nm.
Antireflection, marresistance and the soil resistance of the film manufactured by the manufacture method of one embodiment of the present invention
It is excellent.
Hereinafter, the preferred physical property of the film of the present invention is represented.
(average reflectance changes delta R absolute value)
The antireflection of at least dried coated film in one embodiment of the present invention, can be with by following formula (1)
The light in 400nm~1100nm wavelength of definition represents its property with the absolute value of average reflectance changes delta R during 5 ° of incidence
Energy.
In addition, " at least dried coated film " as long as by the coated film of the drying process, be also included within
Pass through the coated film of the firing process after drying process.
| average reflectance changes delta R |=| R1-R2| formula (1)
In formula (1), R1Represent film formed after base material average reflectance, R2Represent the average reflectance of base material.
It regard barium sulfate blank as the average reflectance (R that the base material for being formed without coated film is determined with reference to sample2) and
Average reflectance (the R of base material with the coated film formed by aqueous coating fluid1), thus, it is possible to obtain the average anti-of formula (1)
Penetrate rate changes delta R.
Reflectivity can be determined by using the spectrophotometer with integrating sphere.Specifically, for example by it is ultraviolet can
See infrared spectrophotometer (JASCO Corporation are manufactured, V-670) etc. and can determine.In the embodiment party of the present invention
In formula, using the light of 400nm~1100nm wavelength, the value of the reflectivity in each wavelength that will be determined using V-670 is calculated
The average value of art, is used as average reflectance.
The numerical value of the average reflectance changes delta R of film absolute value is higher, and antireflection is more excellent.
From the viewpoint of antireflection, the average reflectance changes delta R of coated film absolute value be preferably 2.0% with
On, more preferably more than 2.5%.
(surface roughness Ra)
The surface roughness Ra of the film of one embodiment of the present invention can use AFM (AFM) (Seiko
Instruments Inc. are manufactured, SPA-400) with JIS B0601：(measurement range can be measured on the basis of 2001：3μm
Angle).
The surface roughness Ra of the film of one embodiment of the present invention is preferably below 20nm, more preferably below 10nm.
(water contact angle)
The water contact angle of at least dried coated film in one embodiment of the present invention is preferably less than 40 °, more excellent
Elect less than 30 °, especially preferably more preferably less than 25 °, less than 15 ° as.
Using Kyowa Interface Science Co., the Drop Master 300 of Ltd. manufactures are right to determine 5 times
The contact angle of pure water, water contact angle can be obtained as its average value.
The water contact angle of coated film is set to above range, thus, it is possible to assign sufficient hydrophily to coated film, therefore
The soil resistance of coated film is excellent.
＜ aqueous coating fluids ＞
Aqueous coating fluid is a kind of non-porous the two of below 8nm comprising water, as the average primary particle diameter of silicon dioxide granule
Silicon oxide particle, surfactant, and pH is 1.5~3.5.
Aqueous coating fluid is identical with the implication of the aqueous coating fluid of the manufacture method.By using the implementation of the present invention
The aqueous coating fluid of mode and antireflection, marresistance and the excellent film of soil resistance can be manufactured.
The average primary particle diameter of the preferred nonporous silica silicon particle of aqueous coating fluid is 6nm, and pH is 1.8~3.0.
From the viewpoint of adjustment pH, in aqueous coating fluid, surfactant is preferably nonionic surface active agent.
＜ films ＞
It is the one of below 8nm that the film of one embodiment of the present invention, which contains as the average primary particle diameter of silicon dioxide granule,
Nonporous silica silicon particle is planted, and thickness is more than 50nm and below 350nm.
The system of nonporous silica silicon particle and described an embodiment of the present invention in the film of one embodiment of the present invention
The implication for making nonporous silica silicon particle in method is identical.Antireflection, the scratch resistance of the film of one embodiment of the present invention
Property and soil resistance are excellent.
If the average primary particle diameter of nonporous silica silicon particle is more than 8nm, the film counnter attack of one embodiment of the present invention
Penetrating property is poor.Also, thickness is preferably more than 100nm and below 300nm, more preferably more than 100nm and below 250nm.
From the viewpoint of antireflection, nonporous silica silicon particle in the film of one embodiment of the present invention is averaged
Primary particle size is preferably below 6nm.Average primary particle diameter is more preferably 2nm~4nm.
In the film of one embodiment of the present invention, the light in 400nm~1100nm wavelength defined by following formula (1) with
The absolute value of average reflectance changes delta R during 5 ° of incidence is preferably more than 2.0%, and more preferably more than 2.5%.
| average reflectance changes delta R |=| R1-R2| formula (1)
In formula (1), R1Represent film formed after base material average reflectance, R2Represent the average reflectance of base material.
The film of one embodiment of the present invention can be any of following two modes, from the side of the marresistance of film
Face consideration, preferably the 1st mode.
1st mode is that the state of the particle union body linked with multiple nonporous silica silicon particles contains the nothing in the film
The mode of hole silicon dioxide granule.
Contained nonporous silica silicon particle is the particle union body of multiple nonporous silica silicon particles in film, thus,
While antireflection is kept well, the marresistance of film is further improved.
2nd mode is the film also mode containing surfactant.As such as lower film：Using containing surfactant
The present invention aqueous coating fluid and form coated film, coated film is dried, and is manufactured without the firing process.
＜ layered products ＞
Layered product has the film manufactured by the manufacture method of the one embodiment of the present invention on base material, or
The film of the one embodiment of the present invention.
Therefore the antireflection of layered product, marresistance and soil resistance are excellent.
From the viewpoint of adaptation, the base material in layered product is preferably glass baseplate.
Antireflection, the scratch resistance of the layered product of film with the one embodiment of the present invention formed on the glass substrate
Property and soil resistance be excellent, can be suitably used in such as solar module, CCTV camera and lighting apparatus, label
The purposes such as diaphragm.
＜ solar modules ＞
Solar module possesses layered product, and the layered product has the manufacture by the one embodiment of the present invention
Method and the film manufactured, or the one embodiment of the present invention film.
Solar module is configured to, in of the invention one that the antireflection for the light incident side for being arranged at sunshine is excellent
Between the layered product of embodiment and backboard used for solar batteries by representative of polyester film, configuration turns the luminous energy of sunshine
It is changed to the solar cell device of electric energy.It can be configured between layered product and polyester film for example by with ethylene-acetate second
The resins such as enoate copolymer are sealed for the encapsulant of representative.
On the part in addition to layered product and backboard such as solar module, solar battery cell, in detail
Being recorded in such as " photovoltaic power generation system constituent material ", (China fir this Sakae one is supervized, Kogyo Chosakai Publishing
Co., Ltd., issues for 2008) in.In the solar module of the present invention, preferably possesses this hair in the light incident side of sunshine
Bright layered product, can use arbitrary structure.
As the base material for the light incident side for being arranged at sunshine, it can enumerate transparent such as glass baseplate, acrylic resin
Resin etc., but used in the solar module of one embodiment of the present invention, have in glass substrate surface anti-
The layered product of reflectivity, marresistance, soil resistance also excellent film.
It is without particular limitation as the solar cell device used in solar module, monocrystalline silicon, polysilicon,
The iii-vs such as the silicon such as non-crystalline silicon class, copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, gallium-arsenic and II-VI group compound semiconductor class
It can be applicable etc. various known solar cell devices.
Solar module possesses has antireflection, marresistance and the good film of soil resistance on the glass substrate
Layered product, even if therefore for a long time use, can also suppress because surface film produce scratch or attachment pollutant caused by
Translucency is reduced, and accompanying pollutant is easily removed by water such as rain, therefore through long-time good generating can be maintained to imitate
Rate.
Embodiment
Hereinafter, one embodiment of the present invention is specifically illustrated by embodiment, but the embodiment party of the present invention
Formula would not be defined in following examples without departing from its purport.
(embodiment 1)
(silica dispersions 1A preparation)
Water dispersion NALCO (registration mark) 8699 for adding silicon dioxide granule in deionized water 6.00g
(NALCO companies manufacture, the mass % of solid constituent 15, nonporous silica silicon particle, average primary particle diameter=3nm) 7.02g goes forward side by side
Phosphoric acid is added dropwise in solution obtained from row stirring, pH is adjusted to 1.5~2.0 and silica dispersions 1A is prepared.
In addition, as average primary particle diameter, particle is observed by transmission electron microscope, and by resulting photo
Image obtains the projected area of 300 particles respectively, obtains respectively with the diameter of a circle (equivalent with projected area equal areas
Circular diameter), it regard the value that arithmetic average is carried out to the value of diameter of equivalent circle as average primary particle diameter.
(preparation of aqueous coating fluid 1)
Deionized water 23.5g, ethanol 1.06g and TRITON BG10 (The Dow are added in silica dispersions 1A
Chemical Company are manufactured, nonionic surface active agent) 10 mass % aqueous solution 0.56g, using phosphoric acid by solution
PH be adjusted to 2.4, prepare aqueous coating fluid 1 (the mass % of solid constituent 2.76).
In addition, pH is the value determined using pH instrument (DKK-TOA CORPORATION are manufactured, HM-31P) at 25 DEG C.
(making of membrane sample)
Resulting aqueous coating fluid 1 is coated on glass baseplate using rod coater and coated film is formed.By drying
Case dries the coated film under conditions of 150 DEG C, 1 minute.Afterwards, burnt by electric furnace under conditions of 750 DEG C, 3 minutes
Into producing membrane sample.The final thickness of coated film on glass baseplate turns into 190nm.Also, film is determined by methods described
The result of the surface roughness Ra of sample, surface roughness Ra is below 10nm.
(embodiment 2)
(silica dispersions 1B preparation)
The water dispersion NALCO (registration mark) 8699 of the silica used in embodiment 1 is changed to NALCO
(registration mark) 2326 (NALCO companies manufacture, the mass % of solid constituent 15, nonporous silica silicon particle, average primary particle diameter=
5nm), in addition, silica dispersions 1B is prepared in the same manner as example 1.
(preparation of aqueous coating fluid 2)
The silica dispersions 1A used in embodiment 1 is changed to silica dispersions 1B, and passes through phosphoric acid
PH is adjusted to 2.1, in addition, aqueous coating fluid 2 is prepared in the same manner as example 1.
(making of membrane sample)
The aqueous coating fluid 1 used in embodiment 1 is changed to aqueous coating fluid 2, in addition, with embodiment 1
Identical mode produces membrane sample.Also, the result of the surface roughness Ra of membrane sample is determined by methods described, surface is thick
Rugosity Ra is below 20nm.
(comparative example 1)
(silica dispersions 1C preparation)
The water dispersion NALCO (registration mark) 8699 of the silica used in embodiment 1 is changed to NALCO
(registration mark) 1030 (NALCO companies manufacture, the mass % of solid constituent 15, nonporous silica silicon particle, average primary particle diameter=
13nm), in addition, silica dispersions 1C is prepared in the same manner as example 1.
(preparation of aqueous coating fluid 3)
The silica dispersions 1A used in embodiment 1 is changed to silica dispersions 1C, and passes through phosphoric acid
PH is adjusted to 2.3, in addition, aqueous coating fluid 3 is prepared in the same manner as example 1.
(making of membrane sample)
The aqueous coating fluid 1 used in embodiment 1 is changed to aqueous coating fluid 3, in addition, with embodiment 1
Identical mode produces membrane sample.
(comparative example 2)
(preparation of silica dispersions 1D and aqueous coating fluid 4)
In the adjustment of silica dispersions 1A in embodiment 1, in addition to pH is adjusted into 1.3, with implementation
The identical mode of example 1 prepares silica dispersions 1D, and disperses except silica dispersions 1A is changed into silica
Beyond liquid 1D, aqueous coating fluid 4 is prepared in the same manner as example 1.
(making of membrane sample)
The aqueous coating fluid 1 used in embodiment 1 is changed to aqueous coating fluid 4, in addition, with embodiment 1
Identical mode produces membrane sample.
(comparative example 3)
(preparation of silica dispersions 1E and aqueous coating fluid 5)
In the preparation of silica dispersions 1A in embodiment 1, in addition to pH is adjusted into 3.9, with implementation
The identical mode of example 1 prepares silica dispersions 1E, except silica dispersions 1A is changed into silica dispersions
Beyond 1E, aqueous coating fluid 5 is prepared in the same manner as example 1.
(making of membrane sample)
The aqueous coating fluid 1 used in embodiment 1 is changed to aqueous coating fluid 5, in addition, with embodiment 1
Identical mode produces membrane sample.
(embodiment 3)
(making of membrane sample)
Firing condition in embodiment 1 is changed to 600 DEG C, 3 minutes of condition, in addition, with same as Example 1
Mode produce membrane sample.Also, the result of the surface roughness Ra of membrane sample, surface roughness are determined by methods described
Ra is below 20nm.
(embodiment 4)
(making of membrane sample)
Firing condition in embodiment 1 is changed to 500 DEG C, 3 minutes of condition, in addition, with same as Example 1
Mode produce membrane sample.Also, the result of the surface roughness Ra of membrane sample, surface roughness are determined by methods described
Ra is below 20nm.
(embodiment 5)
(making of membrane sample)
Firing condition in embodiment 1 is changed to 450 DEG C, 3 minutes of condition, in addition, with same as Example 1
Mode produce membrane sample.Also, the result of the surface roughness Ra of membrane sample, surface roughness are determined by methods described
Ra is below 20nm.
(embodiment 6)
(making of membrane sample)
Firing condition in embodiment 1 is changed to the condition of 350 DEG C, 3 points kinds, in addition, with same as Example 1
Mode produce membrane sample.Also, the result of the surface roughness Ra of membrane sample, surface roughness are determined by methods described
Ra is below 20nm.
(comparative example 4)
(preparation of aqueous coating fluid 6)
The TRITON BG10 used in the aqueous coating fluid 1 of embodiment 1 are not added with, and pH is adjusted to 2.3, except this
In addition, aqueous coating fluid 6 is prepared in the same manner as example 1.
(making of membrane sample)
The aqueous coating fluid 1 used in embodiment 1 is changed to aqueous coating fluid 6, in addition, with embodiment 1
Identical mode produces membrane sample.Making the final thickness of membrane sample turns into 190nm.
(comparative example 5)
(silica dispersions 2A preparation (dispersion liquid containing two kinds of silica))
((the NALCO of water dispersion NALCO (registration mark) 8699 for adding silica in deionized water 8.90g
Company manufactures, the mass % of solid constituent 15, nonporous silica silicon particle, average primary particle diameter=3nm) 2.91g and it is stirred
Obtained from phosphoric acid is added dropwise in solution, pH is adjusted to 1.5~2.0 and the 1st dispersion liquid is prepared.
Then, SNOWTEX (registration mark)-UP (NISSAN CHEMICAL are added in deionized water 9.5g
INDUSTRIES, LTD. are manufactured, the mass % of solid constituent 20, beads shape (chain) silicon dioxide granule) 3.2g and it is stirred
Obtained from mixture, be added dropwise 0.1 × 103Mol/L sodium hydroxide, about 12 are adjusted to by pH.Afterwards, ethanol is added dropwise
Aminoethylaminopropyl trimethoxy silane (Dow Corning Toray Co., Ltd.s manufacture, Z-6020) 0.01g in 0.8g,
It is mixed with the pH mixtures for being adjusted to about 12, and stirred 14 hours, the 2nd dispersion liquid is prepared.
1st dispersion liquid and the 2nd dispersion liquid are mixed, silica dispersions 2A is obtained.
(preparation of aqueous coating fluid 7)
Deionized water 12g, ethanol 0.26g and TRITON BG10 10 mass % are added in silica dispersions 2A
Aqueous solution 0.56g, prepares aqueous coating fluid 7 (the mass % of solid constituent 2.82).In addition, the pH of aqueous coating fluid 7 is 2.6.
(making of membrane sample)
The aqueous coating fluid 1 used in embodiment 1 is changed to aqueous coating fluid 7, in addition, with embodiment 1
Identical mode produces membrane sample.Making the final thickness of membrane sample turns into 170nm.
(comparative example 6)
(silica dispersions 2B preparation (dispersion liquid containing two kinds of silica))
(the NALCO public affairs of water dispersion NALCO (registration mark) 8699 for adding silica in deionized water 3.5g
Department manufacture, the mass % of solid constituent 15, nonporous silica silicon particle, average primary particle diameter=3nm) 0.71g and be stirred and
Phosphoric acid is added dropwise in obtained solution, and pH is adjusted into 1.5~2.0 and the 1st dispersion liquid is prepared.
Then, for adding SNOWTEX (registration mark)-UP (NISSAN CHEMICAL in deionized water 15.1g
INDUSTRIES, LTD. are manufactured, the mass % of solid constituent 20, beads shape (chain) silicon dioxide granule) 5.0g and it is stirred
Obtained from mixture, be added dropwise 0.1 × 103Mol/L sodium hydroxide, about 12 are adjusted to by pH.Afterwards, ethanol is added dropwise
Aminoethylaminopropyl trimethoxy silane in 1.3g (Dow Corning Toray Co., Ltd.s manufacture, Z-6020)
0.0015g, it is mixed with the pH mixtures for being adjusted to about 12, and is stirred 14 hours, prepares the 2nd dispersion liquid.
1st dispersion liquid and the 2nd dispersion liquid are mixed, silica dispersions 2B is obtained.
(preparation of aqueous coating fluid 8)
Deionized water 12g and TRITON the BG10 10 mass % aqueous solution are added in silica dispersions 2B
0.56g, thus prepares aqueous coating fluid 8 (the mass % of solid constituent 2.90).The pH of aqueous coating fluid 8 is 8.8.
(making of membrane sample)
The aqueous coating fluid 1 used in embodiment 1 is changed to aqueous coating fluid 8, in addition, with embodiment 1
Identical mode produces membrane sample.Making the final thickness of membrane sample turns into 180nm.
(comparative example 7)
(a kind of silica dispersions 2C preparation (containing dispersion liquid of silica, only beads shape silica))
For adding SNOWTEX (registration mark)-UP (NISSAN CHEMICAL in deionized water 15.9g
INDUSTRIES, LTD. are manufactured, the mass % of solid constituent 20, beads shape (chain) silicon dioxide granule) 5.3g and it is stirred
Obtained from mixture, be added dropwise 0.1 × 103Mol/L sodium hydroxide, about 12 are adjusted to by pH.Afterwards, ethanol 1.3g is added dropwise
In aminoethylaminopropyl trimethoxy silane (Dow Corning Toray Co., Ltd.s manufacture, Z-6020) 0.0016g, will
It is mixed with being adjusted to pH about 12 mixture, and is stirred 14 hours, prepares silica dispersions 2C.
(preparation of aqueous coating fluid 9)
Deionized water 15.1g and TRITON the BG10 10 mass % aqueous solution are added in silica dispersions 2C
0.56g, prepares aqueous coating fluid 9 (the mass % of solid constituent 2.78).The pH of aqueous coating fluid 9 is 9.3.
(making of membrane sample)
The aqueous coating fluid 1 used in embodiment 1 is changed to aqueous coating fluid 9, in addition, with embodiment 1
Identical mode produces membrane sample.Making the final thickness of membrane sample turns into 195nm.
(comparative example 8)
(a kind of silica dispersions 3A preparation (containing dispersion liquid of silica, only beads shape silica))
Using SNOWTEX (registration mark)-OXS (NISSAN CHEMICAL INDUSTRIES, LTD. manufacture, solid into
Divide 10 mass %, beads shape (chain) silicon dioxide granule) and it is used as silica dispersions 3A.
(preparation of aqueous coating fluid 10)
Ethanol 5.15g, 1 matter of double (ethyl acetoacetates) single (acetylacetone,2,4-pentanedione) aluminium are added in deionized water 17.8g
Measure % ethanol solutions 0.60g, polyethyleneglycol lauryl ether (repeat number in oxirane portion is 15) 0.5 mass % aqueous solution
0.94g, two (2- ethylhexyls) sodium sulfosuccinates 0.2 mass the % aqueous solution 0.43g and SNOWTEX (registration mark)-OXS
(NISSAN CHEMICAL INDUSTRIES, LTD. manufactures, the mass % of solid constituent 10, beads shape (chain) titanium dioxide silicon grain
Son) 5.04g and it is stirred, thus prepare aqueous coating fluid 10 (the mass % of solid constituent 1.68).
(making of membrane sample)
The aqueous coating fluid 1 used in embodiment 1 is changed to aqueous coating fluid 10, in addition, with embodiment 1
Identical mode produces membrane sample.Making the final thickness of membrane sample turns into 200nm.
- evaluation of membrane sample-
On above-mentioned resulting each membrane sample, to antireflection (AR：Anti Reflection) it is property, marresistance, antifouling
Property and surface state are evaluated.Evaluation result is shown in table 1 below.
[antireflection (AR) property]
By UV, visible light infrared spectrophotometer (JASCO Corporation are manufactured, V-670), integrating sphere is used
Determine the reflectivity of the light of 400nm~1100nm wavelength of each membrane sample.
When determining reflectivity, for the back side that suppresses glass baseplate with membrane sample, (glass baseplate is formed without
The face of the side of film) reflection, glass substrate surface overleaf pasted black belt.400 as obtained from by measure
The reflectivity of each wavelength in~1100nm wavelength calculates average reflectance, and is calculated according to following formula (1) relative to non-shape
The absolute value (| Δ R |) changed into the average reflectance for the glass baseplate for having film.In addition, | Δ R | numerical value it is higher, antireflection
(AR) property is more excellent.
| average reflectance changes delta R |=| R1-R2| formula (1)
In formula (1), R1Represent film formed after base material average reflectance, R2Represent the average reflectance of base material.
[marresistance 1]
Under 25 DEG C of temperature, the environmental condition of relative humidity 55%, using frictional testing machine, make the film surface of membrane sample to steel
Velvet (manufacture of #0000, NIHON STEEL WOOL Co., Ltd.s) applies 50g loading, and visually observation is with speed 1000mm/
Min carries out the film surface after 10 reciprocating frictions, and marresistance is evaluated according to following metewand.In addition, anti-scratch
A~C of wound property 1 is in permissible range.
- metewand-
A：Do not observe scratch on film surface completely.
B：It is unconfirmed on film surface to arrive scratch, but confirm slight trace.
C：Scratch is confirmed on film surface, the quantity of scratch is 1~20.
D：Scratch is confirmed on film surface, the quantity of scratch is more than 21.
[soil resistance]
Natural sienna (HOLBEIN WORKS, Ltd. manufacture) is set to be evenly distributed and adhere on the film of membrane sample
Afterwards, the back side of membrane sample is patted, shakes off accompanying natural sienna.Repeat 20 operations.Afterwards, visually really
Recognize the attachment state of natural sienna, soil resistance is evaluated according to following metewands.In addition, A~C of soil resistance
In permissible range.
- metewand-
A：In the unattached natural sienna in membrane sample surface, water white transparency.
B：Adhere to some natural siennas on membrane sample surface, it is almost colourless transparent.
C：Adhere to natural sienna in the whole face in membrane sample surface, transparent reduction is able to confirm that by visual observation.
D：Adhere to natural sienna in the whole face in membrane sample surface, it is almost opaque.
[surface state]
The visually surface of observation membrane sample, and being evaluated according to following metewands surface state.
- metewand-
Well：Slightly observe that Gan Wataru are uneven, depression is less than 10/100cm2。
It is bad：Clearly confirm Gan Wataru uneven, be recessed as 10/100cm2More than.
As shown in Table 1, in the membrane sample of embodiment, antireflection, marresistance, soil resistance and surface state are excellent
It is different.
(embodiment 7)
[making of membrane sample]
The aqueous coating fluid 1 in embodiment 1 is coated on glass baseplate using rod coater and coated film is formd.It is logical
Cross baking oven the coated film is dried under conditions of 150 DEG C, 1 minute, membrane sample is set to without burning till.Make membrane sample
Final thickness turn into 190nm.Also, the result of the surface roughness Ra of membrane sample, rough surface are determined by methods described
Degree Ra is below 20nm.
(comparative example 9)
The aqueous coating fluid 10 in comparative example 8 is coated on glass baseplate using rod coater and coated film is formd.
The coated film is dried under conditions of 150 DEG C, 1 minute by baking oven, membrane sample is set to without burning till.Make film sample
The final thickness of product turns into 175nm.
On embodiment 7 and comparative example 9, antireflection, soil resistance and surface have been carried out in the same manner as example 1
The evaluation of state.Evaluation result is shown in table 2 below.
Also, marresistance have rated by the method for following marresistance 2.
[marresistance 2]
Under 25 DEG C of temperature, the environmental condition of relative humidity 55%, make the film surface of membrane sample to steel using frictional testing machine
Velvet (manufacture of #0000, NIHON STEEL WOOL Co., Ltd.s) applies 20g loading, and visually observes with speed
1000mm/min carries out the film surface after 10 reciprocating frictions, and marresistance is have rated according to following metewand.In addition,
A~C of marresistance 2 is in permissible range.
- metewand-
A：Do not observe scratch on film surface completely.
B：It is unconfirmed on film surface to arrive scratch, but confirm slight trace.
C：Scratch is observed on film surface, the quantity of scratch is 1~20.
D：Scratch is confirmed on film surface, the quantity of scratch is more than 21.
[table 2]
As shown in Table 2, the good membrane sample of antireflection can be obtained in embodiment 7, in addition, with comparative example 9
In comparing, the excellent scratch resistance of the membrane sample of embodiment 7.
Japanese patent application 2014-226401 entire disclosures are by reference to quilt filed in 6 days November in 2014
It is incorporated in this specification.
In all documents, patent application and the technical standard recorded in this manual, by reference to and quote each document,
The situation of patent application and technical standard identically with by situation degree that is specific and recording respectively, by reference to and be applied at
In this specification.
Claims (15)
1. a kind of manufacture method of film, it includes：
The process for being coated with aqueous coating fluid on base material and forming coated film, the aqueous coating fluid includes water, is used as titanium dioxide
The average primary particle diameter of silicon particle is a kind of below 8nm nonporous silica silicon particle, surfactant, and the aqueous coating fluid
PH be 1.5~3.5；And
The process that the coated film for being coated with formation is dried.
2. the manufacture method of film according to claim 1, wherein,
The pH is 1.8~3.0.
3. the manufacture method of film according to claim 1 or 2, wherein,
After the process of the coated film is dried, in addition to by dried coated film with more than 400 DEG C and less than 800 DEG C
The process that temperature is burnt till.
4. the manufacture method of film according to claim 3, wherein,
The firing process forms particle union body by burning till, and the particle union body is that multiple nonporous silica silicon particles connect
Knot.
5. the manufacture method of the film according to claim 3 or 4, wherein,
The thickness of the coated film after burning till is more than 50nm and below 350nm.
6. the manufacture method of film according to any one of claim 1 to 5, wherein,
In at least dried coated film, the light in 400nm~1100nm wavelength defined by following formula (1) is entered with 5 °
The absolute value of average reflectance changes delta R when penetrating is more than 2.0%,
| average reflectance changes delta R |=| R1-R2| formula (1)
In formula (1), R1Represent film formed after base material average reflectance, R2Represent the average reflectance of base material.
7. a kind of aqueous coating fluid, a kind of its nothing for being below 8nm comprising water, as the average primary particle diameter of silicon dioxide granule
Hole silicon dioxide granule, surfactant, and the pH of the aqueous coating fluid is 1.5~3.5.
8. aqueous coating fluid according to claim 7, wherein,
The average primary particle diameter is below 6nm.
9. the aqueous coating fluid according to claim 7 or 8, wherein,
The pH is 1.8~3.0.
10. a kind of film, a kind of non-porous silicas that it is below 8nm as the average primary particle diameter of silicon dioxide granule that it, which contains,
Particle, and thickness is more than 50nm and below 350nm.
11. film according to claim 10, wherein,
By the light in 400nm~1100nm wavelength that following formula (1) is defined with the exhausted of average reflectance changes delta R during 5 ° of incidence
It is more than 2.0% to value,
| average reflectance changes delta R |=| R1-R2| formula (1)
In formula (1), R1Represent film formed after base material average reflectance, R2Represent the average reflectance of base material.
12. the film according to claim 10 or 11, wherein,
The nonporous silica silicon particle is contained with the state of particle union body, the particle union body is multiple non-porous silicas
What particle linked.
13. the film according to claim 10 or 11,
The film also contains surfactant.
14. a kind of layered product, has on base material and is manufactured by the manufacture method any one of claim 1 to 6
Film any one of film or claim 10 to 13.
15. a kind of solar module, it possesses the layered product described in claim 14.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014226401A JP2016087561A (en) | 2014-11-06 | 2014-11-06 | Aqueous coating liquid, film, production method of the same, laminate and solar cell module |
| JP2014-226401 | 2014-11-06 | ||
| PCT/JP2015/081383 WO2016072509A1 (en) | 2014-11-06 | 2015-11-06 | Aqueous coating solution, film and manufacturing method therefor, laminate, and solar cell module |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107073520A true CN107073520A (en) | 2017-08-18 |
Family
ID=55909232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580056689.2A Pending CN107073520A (en) | 2014-11-06 | 2015-11-06 | Aqueous coating fluid, film and its manufacture method, layered product and solar module |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2016087561A (en) |
| CN (1) | CN107073520A (en) |
| WO (1) | WO2016072509A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018185865A1 (en) * | 2017-04-04 | 2018-10-11 | パンサーフェス株式会社 | Hydrophilicity-imparting agent, hydrophilic coating film forming method, hydrophilic coating film, and solar panel |
| KR102119717B1 (en) | 2020-03-17 | 2020-06-08 | 주식회사 나온씨에스 | Coating Method and Apparatus for Outdoor Environment to Prevent Contamination of Photovoltaic Modules |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101501130A (en) * | 2006-08-04 | 2009-08-05 | 纳幕尔杜邦公司 | Low refractive index composition |
| CN101579672A (en) * | 2008-05-16 | 2009-11-18 | 3M创新有限公司 | Silicon dioxide coating for improving hydrophilicity/transmittivity |
| CN102241899A (en) * | 2010-05-11 | 2011-11-16 | 3M创新有限公司 | Coating composition, method for modifying matrix surface, and product coated by the coating composition |
| CN102473765A (en) * | 2009-07-08 | 2012-05-23 | 三菱电机株式会社 | Coating agent for solar cell module, and solar cell module and production method for the solar cell module |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012047422A1 (en) * | 2010-10-06 | 2012-04-12 | 3M Innovative Properties Company | Anti-reflective articles with nanosilica-based coatings |
| WO2013127054A1 (en) * | 2012-02-27 | 2013-09-06 | 3M Innovative Properties Company | Basic compositions including inorganic oxide nanoparticles and an organic base, coated substrates, articles, and methods |
-
2014
- 2014-11-06 JP JP2014226401A patent/JP2016087561A/en not_active Abandoned
-
2015
- 2015-11-06 WO PCT/JP2015/081383 patent/WO2016072509A1/en active Application Filing
- 2015-11-06 CN CN201580056689.2A patent/CN107073520A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101501130A (en) * | 2006-08-04 | 2009-08-05 | 纳幕尔杜邦公司 | Low refractive index composition |
| CN101579672A (en) * | 2008-05-16 | 2009-11-18 | 3M创新有限公司 | Silicon dioxide coating for improving hydrophilicity/transmittivity |
| CN102473765A (en) * | 2009-07-08 | 2012-05-23 | 三菱电机株式会社 | Coating agent for solar cell module, and solar cell module and production method for the solar cell module |
| CN102241899A (en) * | 2010-05-11 | 2011-11-16 | 3M创新有限公司 | Coating composition, method for modifying matrix surface, and product coated by the coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2016087561A (en) | 2016-05-23 |
| WO2016072509A1 (en) | 2016-05-12 |
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Application publication date: 20170818 |