CN106999982A - 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
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- CN106999982A CN106999982A CN201580065615.5A CN201580065615A CN106999982A CN 106999982 A CN106999982 A CN 106999982A CN 201580065615 A CN201580065615 A CN 201580065615A CN 106999982 A CN106999982 A CN 106999982A
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- China
- Prior art keywords
- coating fluid
- aqueous coating
- film
- silicon dioxide
- coated film
- Prior art date
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- 238000000576 coating method Methods 0.000 title claims abstract description 334
- 239000011248 coating agent Substances 0.000 title claims abstract description 332
- 239000012530 fluid Substances 0.000 title claims abstract description 301
- 238000000034 method Methods 0.000 title claims abstract description 104
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 88
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 434
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 216
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 174
- 239000008187 granular material Substances 0.000 claims abstract description 171
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000011164 primary particle Substances 0.000 claims abstract description 67
- 229920005862 polyol Polymers 0.000 claims abstract description 65
- 150000003077 polyols Chemical class 0.000 claims abstract description 65
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 64
- 239000000463 material Substances 0.000 claims abstract description 44
- 238000001035 drying Methods 0.000 claims abstract description 31
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims description 68
- -1 alkyl poly glucoside Chemical class 0.000 claims description 35
- 239000011521 glass Substances 0.000 claims description 32
- 239000004094 surface-active agent Substances 0.000 claims description 31
- 229930182478 glucoside Natural products 0.000 claims description 27
- 238000010304 firing Methods 0.000 claims description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 238000002310 reflectometry Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000010408 film Substances 0.000 description 269
- 239000012528 membrane Substances 0.000 description 101
- 239000000470 constituent Substances 0.000 description 41
- 239000002689 soil Substances 0.000 description 31
- 239000006185 dispersion Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 23
- 239000012298 atmosphere Substances 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- 239000000126 substance Substances 0.000 description 21
- 239000002245 particle Substances 0.000 description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 19
- 229910052710 silicon Inorganic materials 0.000 description 19
- 239000010703 silicon Substances 0.000 description 19
- 230000000007 visual effect Effects 0.000 description 18
- 239000011856 silicon-based particle Substances 0.000 description 16
- 238000005755 formation reaction Methods 0.000 description 15
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007859 condensation product Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 7
- 230000005611 electricity Effects 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002519 antifouling agent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 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 4
- 238000005259 measurement Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 150000008131 glucosides Chemical class 0.000 description 3
- 239000011859 microparticle Substances 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229940088594 vitamin Drugs 0.000 description 3
- 229930003231 vitamin Natural products 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000003373 anti-fouling effect Effects 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
- 239000000919 ceramic Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000000733 zeta-potential measurement Methods 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-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
- 241000208340 Araliaceae Species 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000050510 Cunninghamia lanceolata Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 description 1
- 229940073499 decyl glucoside Drugs 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005591 polysilicon Polymers 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
- 230000001846 repelling effect Effects 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 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
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to a kind of manufacture method of film and its application, the manufacture method of the film includes：Coated film formation process, is coated with aqueous coating fluid on base material and forms coated film, and the aqueous coating fluid includes water, the electronegative silicon dioxide granule in surface, the polyol-based non-ionic surfactant that average primary particle diameter is below 8nm, and pH is 8~12；And coated film drying process, 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, for example, it can enumerate antireflection film, optical lens, optics
Thin film transistor (TFT) planarization film, anti-condensation film, anti-soil film and the surface protection film of filter, various displays
Deng.Wherein, antireflection film and anti-soil film are because that can be used in such as solar module, CCTV camera, lighting apparatus, mark
Label etc. diaphragm and it is useful.
On the aqueous coating fluid containing silicon dioxide microparticle for the purposes for being used in anti-soil film etc., in recent years, it has been suggested that
There are various schemes.
For example, the nonpolluting coating liquid that there is the film coated surface for repelling property as can equably be coated on aqueous solution,
Proposition, which has, contains silicon dioxide microparticle, water and surfactant as neccessary composition, and contains substantially no the nonpolluting coating of alcohol
Liquid (for example, with reference to Japan Patent 2010-138358 publications).
Also, as the anti-fouling effect to hard surface it is excellent and also have washable effect anti-fouling agent, proposition have containing
The average grain diameter of positively charged is 1nm~100nm silica-based compound and the hard surface anti-fouling agent of water (for example, ginseng
Examine Japanese Unexamined Patent Publication 2002-3820 publications).
The content of the invention
The invention technical task to be solved
But, the diaphragm of solar module, CCTV camera for being disposed in the outdoor long-term use etc., not only
It is required that soil resistance, also requires antireflection and scratch resistance.
However, being applied by using formed by the nonpolluting coating liquid being recorded in Japan Patent 2010-138358 publications
Film surface has a sufficient soil resistance, but antireflection and scratch resistance and insufficient.Also, using being recorded in Japanese Unexamined Patent Publication
Film coated surface formed by anti-fouling agent in 2002-3820 publications has sufficient soil resistance, but antireflection and damage resistant
Property is poor.
That is, under actual conditions, antireflection, scratch resistance and anti-fouling agent excellent film are not provided with.
One embodiment of the present invention be in view of above-mentioned actual conditions and complete, its problem be provide one kind can be formed
The aqueous coating fluid of antireflection, scratch resistance and the excellent film of soil resistance.
Also, the problem of one embodiment of the present invention is to provide a kind of antireflection, scratch resistance and soil resistance excellent
Different film and its manufacture method, layered product and solar module.
Means for solving technical task
Mode for solving problem includes in the following manner.
[1] a kind of manufacture method of film, it includes：Coated film formation process, is coated with aqueous coating fluid and shape on base material
Into coated film, the aqueous coating fluid includes water, the electronegative titanium dioxide silicon grain in surface that average primary particle diameter is below 8nm
Son, polyol-based non-ionic surfactant, and pH is 8~12；And coated film drying process, the coated film for being coated with formation is entered
Row drying.
[2] manufacture method of the film according to [1], the average primary particle diameter of silicon dioxide granule is below 6nm.
[3] manufacture method of the film according to [1] or [2], the pH of aqueous coating fluid is 9~11.
[4] according to the manufacture method of the film described in any of [1]~[3], polyol type in aqueous coating fluid it is non-from
The content of sub- surfactant is the mass % of 0.07 mass %~1.0 relative to the gross mass of aqueous coating fluid.
[5] according to the manufacture method of the film described in any of [1]~[4], polyol-based non-ionic surfactant is
With polyol-based non-ionic surfactant of the cyclic polyether as hydrophilic radical.
[6] according to the manufacture method of the film described in any of [1]~[5], polyol-based non-ionic surfactant is
Alkyl poly glucoside class surfactant.
[7] manufacture method of the film according to any of [1]~[6], after coated film drying process, in addition to
The coated film firing process that dried coated film is burnt till with the temperature of more than 400 DEG C and less than 800 DEG C.
[8] by dried coated film with 500 DEG C in the manufacture method of the film according to [7], coated film firing process
Above and less than 800 DEG C of temperature is burnt till.
[9] manufacture method of the film according to [7] or [8], after coated film drying process, coated film firing process
The content of the silicon dioxide granule in coated film before is the matter of 64 mass %~95 relative to the total solid content of coated film
Measure %.
[10] manufacture method of the film according to any of [7]~[9], the thickness of the coated film after burning till is 50nm
Above and below 350nm.
[11] in the manufacture method of the film according to any of [1]~[10], at least dried coated film, under
State the light in 400nm~1100nm wavelength that formula (1) defines using the absolute value of average reflectance changes delta R during 5 ° of incidence as
More than 2.0%.
| average reflectance changes delta R |=| RFilm formed after base material average reflectance-RThe average reflectance of base material| formula (1)
[12] manufacture method of the film according to [11], average reflectance changes delta R absolute value is more than 2.5%.
[13] a kind of aqueous coating fluid, includes water, the electronegative silica in surface that average primary particle diameter is below 8nm
Particle, polyol-based non-ionic surfactant, and pH is 8~12.
[14] aqueous coating fluid according to [13], the average primary particle diameter of silicon dioxide granule is below 6nm.
[15] aqueous coating fluid according to [13] or [14], the pH of aqueous coating fluid is 9~11.
[16] silicon dioxide granule in the aqueous coating fluid according to any of [13]~[15], aqueous coating fluid
Content relative to the total solid content of aqueous coating fluid be the mass % of 64 mass %~95.
[17] according to the aqueous coating fluid described in any of [13]~[16], polyol type in aqueous coating fluid it is non-from
The content of sub- surfactant is the mass % of 0.07 mass %~1.0 relative to the gross mass of aqueous coating fluid.
[18] according to the aqueous coating fluid described in any of [13]~[17], polyol-based non-ionic surfactant is
With polyol-based non-ionic surfactant of the cyclic polyether as hydrophilic radical.
[19] according to the aqueous coating fluid described in any of [13]~[18], polyol-based non-ionic surfactant is
Alkyl poly glucoside class surfactant.
[20] a kind of film, is manufactured by the manufacture method described in any of [1]~[12].
[21] a kind of layered product, has the film described in [20] on base material.
[22] layered product according to [21], base material is glass baseplate.
[23] a kind of solar module, possesses the layered product described in [21] or [22].
Invention effect
According to an embodiment of the present invention, using the teaching of the invention it is possible to provide antireflection, scratch resistance and soil resistance can be formed excellent
The aqueous coating fluid of film.
Also, according to an embodiment of the present invention, using the teaching of the invention it is possible to provide antireflection, scratch resistance and the excellent film of soil resistance
And its manufacture method, layered product and solar module.
Brief description of the drawings
Fig. 1 is that the electron microscope of the surface state equivalent to metewand [A] in the evaluation test of surface state shines
Piece.
Fig. 2 is that the electron microscope of the surface state equivalent to metewand [E] in the evaluation test of surface state shines
Piece.
Embodiment
Hereinafter, the embodiment on the present invention is described in detail, but the present invention is not limited to following implementation
Mode, suitably can be changed and be implemented in the range of the purpose of the present invention.
In this manual, the number range represented with "~" refers to the numerical value that will be recorded in before and after "~" as most
It is small value and maximum and comprising scope.
In this manual, in the case of there are a variety of materials equivalent to each composition in the composition, if without special
Illustrate, then the amount of each composition in composition refers to be present in the total amount of many kinds of substance in composition.
In this manual, the term of " process " not only includes independent process, and even in can not with other processes
If can clearly realize the expected purpose of the process in the case of Qu Do, it can also be included in the term.
[manufacture method of film]
The manufacture method of the film of the disclosure includes：Coated film formation process, is coated with aqueous coating fluid on base material and is formed
Coated film, the aqueous coating fluid comprising water, average primary particle diameter for below 8nm the electronegative silicon dioxide granule in surface,
Polyol-based non-ionic surfactant, and pH is 8~12；And coated film drying process, the coated film for being coated with formation is carried out
Dry.
The manufacture method of the film of the disclosure after coated film drying process, preferably also include by dried coated film with
The coated film firing process that more than 400 DEG C and less than 800 DEG C of temperature is burnt till.Also, the manufacture method of the film of the disclosure
In the range of the effect of the disclosure is not damaged, as needed, other processes can also be included.
In the manufacture method of the film of the disclosure, it is coated with aqueous coating fluid on base material and is formed after coated film, will be applied
The coated film of cloth formation is dried, described aqueous thus, it is possible to obtain antireflection, scratch resistance and the excellent film of soil resistance
Coating fluid includes water, the electronegative silicon dioxide granule in surface, the polyol type nonionic table that average primary particle diameter is below 8nm
Face activating agent, and pH is 8~12.
Although passing through the antireflection of film obtained from the manufacture method of the disclosure, scratch resistance and the excellent reason of soil resistance
By and it is indefinite, but the present inventor etc. is carried out as follows supposition.
If being coated with the aqueous coating fluid comprising silicon dioxide granule on base material and drying it, titanium dioxide silicon grain is formed
The film of sub local adhesion each other.Film formed by local adhesion has the production between silicon dioxide granule to silicon dioxide granule each other
Raw space, it is taken as that antireflection is excellent.
Fine silicon dioxide granule easily condenses in the solution.If the use of comprising average primary particle diameter being below 8nm's
The electronegative silicon dioxide granule in surface, and control be have gap with the isoelectric point (pH4~6) of silicon dioxide granule pH (8~
12) aqueous coating fluid, then can suppress the cohesion of the silicon dioxide granule in aqueous coating fluid, the dispersiveness of silicon dioxide granule
Become good.If the dispersiveness of silicon dioxide granule becomes good, the coating accuracy of aqueous coating fluid is improved, it is taken as that institute
The antireflection of the film of formation is excellent.
The electronegative silicon dioxide granule in surface of particle repels each other and is intended to maintain dispersiveness, but coexists in aqueous coating
Polyol-based non-ionic surfactant in liquid has the property on the surface for being difficult to be adsorbed in silicon dioxide granule, therefore, it is difficult to
Damage the dispersiveness of silicon dioxide granule.On the other hand, polyol-based non-ionic surfactant is local in aqueous coating fluid
It is present in the surface of solution, can be to reduce the surface tension of aqueous coating fluid, therefore the wetability of aqueous coating fluid on a small quantity
Become good.According to the effect of this polyol-based non-ionic surfactant, coated film evenly can be formed, it is believed that can
To obtain excellent antireflection.
If coating includes aqueous coating of the average primary particle diameter for below 8nm fine silicon dioxide granule on base material
Liquid simultaneously dries it, then silicon dioxide granule is closely configured, and forms fine and close film, therefore the hardness of film is improved, it is believed that can be with
Obtain excellent scratch resistance.If in addition, burning till by dry coated film, the local adhesion between particle becomes more firmly,
And film becomes fine and close, it is taken as that scratch resistance is further improved.
Also, the smoothened result of film surface by formation fine and close film, can suppress the attachment of dirt, it is believed that can obtain
To excellent soil resistance.
By above content, it is believed that the film manufactured by the manufacture method of the disclosure is in antireflection, scratch resistance and prevents
It is excellent in dirt.
Hereinafter, it is described in detail on each operation in the manufacture method of the film of the disclosure.On being used in each operation
Composition etc. detailed content carry out it is aftermentioned.
(coated film formation process)
Coated film formation process is the process that coating aqueous coating fluid forms coated film on base material, the aqueous coating fluid
Include water, the electronegative silicon dioxide granule in surface, the polyol type non-ionic surface active that average primary particle diameter is below 8nm
Agent, and pH is 8~12.
In coated film formation process, as foregoing, using the aqueous coating fluid of the favorable dispersibility of silicon dioxide granule,
It is taken as that can be with good coating accuracy formation coated film.Also, the aqueous coating used in coated film formation process
Liquid is included to have and locally lain in the polyol-based non-ionic surfactant of the tendency of solution surface, therefore wetability becomes good
It is good, it is believed that coated film evenly can be formed.
The coating weight of aqueous coating fluid the concentration of the solid constituent in aqueous coating fluid, is wished without special restriction
Thickness of prestige etc., it is considered to operability wait and can suitably set.The coating weight of aqueous coating fluid is preferably 0.1mL/m2~
1000mL/m2, more preferably 1mL/m2~100mL/m2, more preferably 1mL/m2~50mL/m2.If the painting of aqueous coating fluid
Within the above range, then coating accuracy becomes good to cloth amount, can form the more excellent film of antireflection.
The method of aqueous coating fluid is coated with base material without special restriction.As coating method, can be applicable spraying,
Coating method known to brushing, roller coat, rod painting, dip-coating etc..
(coated film drying process)
Coated film drying process is the process that the coated film for being coated with formation is dried.
In coated film drying process, coated film formed by coating aqueous coating fluid is dried, thus in base material
The upper film for forming silicon dioxide granule local adhesion each other.If silicon dioxide granule local adhesion each other, in titanium dioxide silicon grain
Space is produced between son, it is taken as that excellent by the antireflection of dry coated film.
Also, in coated film drying process, it will be applied in coated film formation process with high accuracy and be formed more
Uniform coated film is dried, it is taken as that the antireflection of dried coated film is excellent.
In coated film drying process, the moisture in aqueous coating fluid is removed, and thus silicon dioxide granule is by closely
Configuration, forms fine and close film.Film becomes fine and close and hardness raising, it is thus regarded that can obtain excellent scratch resistance.Also, film becomes
It is fine and close and film surface is smoothened, thus dirt is difficult to adhere to, it is believed that can obtain excellent soil resistance.
The drying of coated film can be carried out under room temperature (25 DEG C), can also use heater to carry out.It is used as heating
Device, as long as target temperature can be heated to, is then not particularly limited, and can use known heater.As
Heater, in addition to baking oven, electric furnace etc., additionally it is possible to heater independently made using cooperation production line etc..
For example, it is also possible to using above-mentioned heater, coated film is heated at 40 DEG C~400 DEG C of atmosphere temperature, is thus entered
The drying of row coated film.In the case of the drying coating film by heating, for example, the heat time can be set to 1 minute~
30 minutes or so.
As the drying condition of coated film, preferably by coated film at 40 DEG C~200 DEG C of atmosphere temperature through 1 minute~10 points
The drying condition that clock is heated, it is dry through what is heated within 1 minute~5 minutes more preferably at 100 DEG C~180 DEG C of atmosphere temperature
Dry condition.
The thickness of dried coated film is preferably more than 50nm.If thickness is more than 50nm, dried coated film
Antireflection it is more excellent.
The thickness of dried coated film is more preferably more than 50nm and below 350nm, further preferred more than 100nm
Below 300nm, especially preferably more than 100nm below 250nm.
After coated film drying process, in the coated film before coated film firing process, average primary particle diameter is 8nm
The content of the electronegative silicon dioxide granule in following surface, relative to coated film total solid content be preferably 64 mass %~
The mass % of 95 mass %, more preferably 70 mass %~95.If providing into the dried coated film of coated film firing process
, average primary particle diameter for below 8nm the electronegative silicon dioxide granule in surface content within the above range, then being capable of shape
Into antireflection, scratch resistance and the more excellent film of soil resistance.
(coated film firing process)
The manufacture method of the film of the disclosure, preferably after foregoing coated film drying process, in addition to by it is dried apply
The coated film firing process that cloth film is burnt till with the temperature of more than 400 DEG C and less than 800 DEG C of atmosphere temperature.
In coated film firing process, by dried coated film with the temperature of more than 400 DEG C and less than 800 DEG C of atmosphere temperature
Degree is burnt till, and the hardness of the fine and close film thus formed in coated film drying process is further improved, and scratch resistance enters
One step is improved, and is partially formed small space because organic principle disappears, therefore antireflection is significantly improved.
Burning till for coated film can use heater to carry out.As heater, as long as mesh can be heated into
Temperature is marked, then without special restriction, can use known heater.As heater, in addition to electric furnace etc., also
The burning apparatus for coordinating production line independently to make can be used.
The firing temperature (atmosphere temperature) of coated film is more preferably more than 450 DEG C and less than 800 DEG C, more preferably
More than 500 DEG C and less than 800 DEG C, especially preferably more than 600 DEG C and less than 800 DEG C.Firing time is preferably 1 minute~10 points
Clock, more preferably 1 minute~5 minutes.
The thickness of coated film after burning till is preferably more than 50nm.If thickness is more than 50nm, the coated film after burning till
Antireflection it is more excellent.
The thickness of coated film after burning till is more preferably more than 50nm and below 350nm, more preferably more than 100nm
And below 300nm, especially preferably more than 100nm and below 250nm.
(other processes)
The manufacture method of the film of the disclosure as needed, can also include in the range of the effect of the present invention is not damaged
Other processes.
As other processes, matting, surface treatment procedure and refrigerating work procedure etc. can be enumerated.
Hereinafter, it is described in detail on composition for being used in each operation in the manufacture method of the film of the disclosure etc..
＜ base materials ＞
In the manufacture method of the film of the disclosure, there is no particular limitation for the base material of coating aqueous coating fluid.As base material,
The base materials such as glass, resin, metal, ceramics and their composite can be enumerated, these base materials suitably can enter to exercise
With.Wherein, as base material, preferred glass baseplate.If using glass baseplate as base material, not only in silicon dioxide granule institute
Between the hydroxyl having, and hydroxyl is also produced between the hydroxyl and the hydroxyl of glass surface that silicon dioxide granule has
The condensation of base, therefore, it is possible to form the coated film with the excellent adhesion of base material.
＜ aqueous coating fluids ＞
Aqueous coating fluid in the manufacture method of the film of the disclosure includes water, the surface that average primary particle diameter is below 8nm
Electronegative silicon dioxide granule, polyol-based non-ionic surfactant, and pH is 8~12.
According to aqueous coating fluid, antireflection, scratch resistance and soil resistance excellent film can be formed.
Aqueous coating fluid is because that can form the excellent film of antireflection comprising silicon dioxide granule.
If being coated with base material aqueous coating fluid and dries it, silicon dioxide granule local adhesion each other is formed and existed
There is the perforated membrane in space between silicon dioxide granule.Think the antireflection of film becomes excellent by the space.
Also, aqueous coating fluid includes the electronegative silicon dioxide granule in surface that average primary particle diameter is below 8nm, and
The pH (8~12) for having gap for the isoelectric point (pH4~6) with silicon dioxide granule is controlled, it is excellent therefore, it is possible to form antireflection
Different film.
By the way that aqueous coating fluid of the average primary particle diameter for below the 8nm electronegative silicon dioxide granule in surface will be included
PH be set to the pH for having gap with the isoelectric point of silicon dioxide granule, the cohesion of fine silicon dioxide granule can be suppressed, it is believed that
Silicon dioxide granule disperses well.The coating accuracy for the aqueous coating fluid that silicon dioxide granule disperses well is excellent, therefore
Think that the antireflection of formed film is excellent.
In addition, aqueous coating fluid includes polyol-based non-ionic surfactant, it is excellent therefore, it is possible to form antireflection
Film.
As foregoing, polyol-based non-ionic surfactant has the property for being difficult to be adsorbed in silica particle surface
Matter, it is difficult to damage the dispersiveness of silicon dioxide granule.Also, polyol-based non-ionic surfactant can be reduced with a small amount of
The surface tension of aqueous coating fluid, it is taken as that the wetability of aqueous coating fluid becomes good.The wetability of aqueous coating fluid becomes
Obtain well, thus the uniformity of formed film is improved, it is believed that the antireflection of film becomes excellent.
Aqueous coating fluid includes the fine silicon dioxide granule that average primary particle diameter is below 8nm, therefore, it is possible to be formed
Scratch resistance and the excellent film of soil resistance.
If aqueous coating fluid includes fine silicon dioxide granule, when being coated with and drying it, silicon dioxide granule
Closely configure, the high fine and close film of hardness can be formed, it is taken as that the scratch resistance of formed film becomes excellent.Also,
The film surface for the fine and close film that silicon dioxide granule is closely configured is smoothened, it is taken as that the soil resistance of formed film becomes excellent
It is different.
(silicon dioxide granule)
Aqueous coating fluid includes the electronegative silicon dioxide granule in surface that average primary particle diameter is below 8nm.
The average primary particle diameter of silicon dioxide granule is preferably below 8nm and below 6nm, more preferably more than 2nm and 4nm
Below.If the average primary particle diameter of silica is below 8nm, antireflection and the excellent film of scratch resistance are formed.
Scattered silicon dioxide granule is observed by transmission electron microscope, can by captured photo image
Obtain the average primary particle diameter of silicon dioxide granule particle.Specifically, by photo determining image silicon dioxide granule throwing
Shadow area, diameter of equivalent circle is obtained by the projected area determined, will be calculated by the value to calculated diameter of equivalent circle
Value obtained from art is average is set to the average primary particle diameter of silicon dioxide granule.Silicon dioxide granule in this specification is averaged
Primary particle size determines the projected area of 300 silicon dioxide granules respectively using following value, is integrated by the perspective plane determined
Diameter of equivalent circle is not obtained, carries out being worth obtained from arithmetic average by the value to diameter of equivalent circle.
There is no particular limitation for the species of silicon dioxide granule included in aqueous coating fluid.It is used as titanium dioxide silicon grain
Son, can enumerate hollow silica particle, porous silica silicon particle, nonporous silica silicon particle etc..
There is no particular limitation for the shape of silicon dioxide granule.It can be the arbitrary shape such as spherical, ellipticity, chain.
Also, silicon dioxide granule can also be the silicon dioxide granule that surface is handled using aluminium compound etc..
As the silicon dioxide granule included in aqueous coating fluid, the preferred nonporous silica silicon particle in above-mentioned.
" nonporous silica silicon particle " refers to the silicon dioxide granule for not having space in the inside of particle, is different from
The inside of the particles such as empty silicon dioxide granule and porous silica silicon particle has the silicon dioxide granule in space.In addition, " non-porous
Do not include the silicon dioxide granule of following nucleocapsid structure in silicon dioxide granule "：There is the cores such as polymer in the inside of particle,
The shell (shell) of core by silica or silica precursor (for example, raw material by burning till and becoming silica) structure
Into.
Nonporous silica silicon particle is before and after coated film firing process, and the state for being present in the particle in coated film occurs
Change.Specifically, in the coated film before burning till, each nonporous silica silicon particle is as single particle (in this specification
In, it regard the state of the set such as the state condensed by Van der Waals for as single particle.) and exist, after burning till
In coated film, at least a portion in multiple nonporous silica silicon particles exists as particle union body connected to each other.
If the silicon dioxide granule included in aqueous coating fluid is nonporous silica silicon particle, pass through the burning of coated film
Into multiple nonporous silica silicon particles are concatenated and form particle union body, therefore the hardness of film is improved, and scratch resistance is further
Improve.
Used by the average primary particle diameter for the particle for burning till and linking, linking part (for example, neck portion) do not considered,
And value obtained from diameter when ball is assumed to one in the particle that is concatenated only is carried out into arithmetic average.By burning till and
The average primary particle diameter of the particle of link can be by calculating with the average primary particle diameter identical method of aforementioned silicas particle
Go out.
Aqueous coating fluid can also include the different silicon dioxide granule of a variety of primary particle sizes.Also, aqueous coating fluid
Can be comprising more than a kind silicon dioxide granule beyond nonporous silica silicon particle and nonporous silica silicon particle.
Silicon dioxide granule can use commercially available product.As the example of commercially available product, NALCO (registration mark) can be enumerated
8699 (water dispersions of nonporous silica silicon particle, average primary particle diameter：3nm, solid constituent：15 mass %, NALCO companies
Manufacture), NALCO (registration mark) 1130 (water dispersion of nonporous silica silicon particle, average primary particle diameter：8nm, solid into
Point：30 mass %, NALCO companies manufacture), SNOWTEX (registration mark) XS (water dispersion of nonporous silica silicon particle, put down
Equal primary particle size：5nm, solid constituent：20 mass %, NISSAN CHEMICAL INDUSTRIES, LTD. manufactures) etc..
Average primary particle diameter contained by aqueous coating fluid is negatively charged for the surface of below 8nm silicon dioxide granule.
Dispersion stabilization of the electronegative silicon dioxide granule in surface in aqueous coating fluid is good.If in aqueous coating fluid
Silicon dioxide granule dispersion stabilization it is good, then coating accuracy becomes good, can form the excellent film of antireflection.And
And, the film of good surface state (appearance) can be formed.
The electriferous state of silicon dioxide granule included in aqueous coating fluid is able to confirm that by determining Zeta potential.
Specifically, in the state of pH is maintained, aqueous coating fluid is suitably diluted using deionized water, on resulting aqueous painting
The diluent determining Zeta potential of cloth liquid, in the case where measurement result is bears, it is " negative " to be set to silicon dioxide granule powered,
Measurement result is powered for " just " in the case of just, to be set to silicon dioxide granule.As the measure device of Zeta potential, it can make
With such as Zeta potential measurement system (model：ELSZ-1, OTSUKA ELECTRONICS Co., LTD manufacture).
The content phase for the electronegative silicon dioxide granule in surface that average primary particle diameter in aqueous coating fluid is below 8nm
Total solid content for aqueous coating fluid is preferably the mass % of 64 mass %~95, the matter of more preferably 70 mass %~95
Measure %.
If the electronegative silicon dioxide granule in surface that the average primary particle diameter included in aqueous coating fluid is below 8nm
Ratio reduce, then the composition beyond the silicon dioxide granule ratio regular meeting increase.For example, being lived in polyol type non-ionic surface
Property agent ratio it is increased in the case of, average primary particle diameter for below 8nm the electronegative silicon dioxide granule in surface surface
Easily coated by polyol-based non-ionic surfactant, thus the dispersiveness reduction of the silicon dioxide granule, it is difficult to obtain
The good surface state such as the condensation product of silicon dioxide granule can be confirmed on film surface.On the other hand, if institute in aqueous coating fluid
Comprising average primary particle diameter for below 8nm the electronegative silicon dioxide granule in surface ratio increase, then it is relatively polynary
The ratio regular meeting of alcohol type nonionic surfactant is reduced, therefore based on film and the counnter attack for burning till and being formed good surface state
The effect that penetrating property raising etc. is produced by polyol-based non-ionic surfactant is reduced.
If the content for the electronegative silicon dioxide granule in surface that the average primary particle diameter in aqueous coating fluid is below 8nm
Total solid content relative to aqueous coating fluid is more than 64 mass %, then can form the more excellent grade of scratch resistance better
The film of film quality.
If the content for the electronegative silicon dioxide granule in surface that the average primary particle diameter in aqueous coating fluid is below 8nm
Total solid content relative to aqueous coating fluid is below 95 mass %, then can form better by burning till for coated film
Surface state film.
In addition, the average primary particle diameter in aqueous coating fluid is below the 8nm electronegative silicon dioxide granule in surface
Content is preferably more preferably below 10 mass % below 15 mass % relative to the gross mass of aqueous coating fluid, further excellent
Elect as below 6 mass %.
If the content for the electronegative silicon dioxide granule in surface that the average primary particle diameter in aqueous coating fluid is below 8nm
Gross mass relative to aqueous coating fluid is below 15 mass %, then average primary particle diameter is electronegative for below 8nm surface
Dispersiveness raising of the silicon dioxide granule in aqueous coating fluid, therefore be in terms of the cohesion of the silicon dioxide granule is prevented
Favourable.
Also, the average primary particle diameter in aqueous coating fluid is below the 8nm electronegative silicon dioxide granule in surface
Content is preferably more than 0.1 mass % more preferably more than 0.5 mass % relative to the gross mass of aqueous coating fluid, further
Preferably more than 1 mass %.
If the content for the electronegative silicon dioxide granule in surface that the average primary particle diameter in aqueous coating fluid is below 8nm
Gross mass relative to aqueous coating fluid is more than 0.1 mass %, then for obtain desired dried thickness and needed for liquid
Coating weight will not excessively increase, therefore drying load is inhibited.
(polyol-based non-ionic surfactant)
Aqueous coating fluid comprises at least a kind of polyol-based non-ionic surfactant.
In aqueous coating fluid, polyol-based non-ionic surfactant be difficult to be adsorbed in average primary particle diameter for 8nm with
Under the electronegative silicon dioxide granule in surface surface, and be present in the near surface of solution, therefore the profit of aqueous coating fluid
It is moist to improve, uniform film can be formed.So as to which aqueous coating fluid passes through the energy comprising polyol-based non-ionic surfactant
Enough form the excellent film of antireflection.Also, the shape using the aqueous coating fluid comprising polyol-based non-ionic surfactant
Into coated film, by burning till and the surface state of film becomes good.
" polyol-based non-ionic surfactant " refers to such as anionic surfactant, cationic surface active agent
And amphoteric surfactant does not include the part for carrying out ionic dissociation and the surfactant with multiple hydroxyls like that.As many
First alcohol type nonionic surfactant, and have with cyclic polyether as the nonionic surfactant of the structure of hydrophilic radical
Sorbitan fatty ester, sucrose fatty ester, alkyl poly glucoside etc., also, as without cyclic polyether knot
The nonionic surfactant of structure, there is fatty acid glyceride, the alkyl fatty esters of polyglycereol, alkyl glycerylether, Sorbitan
The nonionic surfactants such as sugar alcohol.
Wherein, as polyol-based non-ionic surfactant, from the sight for the film that can form better surface state
Point considers, preferably with nonionic surfactant of the cyclic polyether as hydrophilic radical.In addition, from can be formed have it is more excellent
From the viewpoint of different antireflection and the film of soil resistance, as polyol-based non-ionic surfactant, more preferably alkyl gathers
Glucoside.
The carbon number of the alkyl chain of alkyl poly glucoside is preferably 5~20, and more preferably 6~14, further preferably
For 8~14.The alkyl chain of alkyl poly glucoside can be straight-chain or branched.The average polymerization of glucoside
Degree is preferably 1~10, more preferably 1~5.As the concrete example of alkyl poly glucoside, decyl glucoside can be enumerated, pungent
Base glucoside etc..
The weight average molecular weight of alkyl poly glucoside is preferably 100~2000, and more preferably 100~1000.
Polyol-based non-ionic surfactant can also use commercially available product.As the example of commercially available product, it can enumerate
TRITON (registration mark) BG-10 (alkyl poly glucoside class surfactant, The Dow Chemical Company systems
Make), MYDOL (registration mark) 10,12 (alkyl poly glucoside class surfactant, Kao Corporation manufacture),
RHEODOL (registration mark) SP-P10 (sorbitan fatty ester class surfactant, Kao Corporation systems
Make), RIKEMAL (registration mark) L-71-D (two glycerine fatty acid esters surfactants, RIKEN VITAMIN CO., LTD.
Manufacture), EXCEL (registration mark) 95N (fatty acid glyceride, Kao Corporation manufacture), POEM (registration mark) PR-
100 (alkyl glycerylether, RIKEN VITAMIN CO., LTD. manufactures), DK Ester (registration mark) (sucrose fatty ester,
DKS Co.Ltd. are manufactured) etc..
Gross mass of the content of polyol-based non-ionic surfactant in aqueous coating fluid relative to aqueous coating fluid
The mass % of preferably 0.07 mass %~1.0 mass %, more preferably 0.07 mass %~0.8, more preferably 0.07 matter
Measure the mass % of %~0.5.
If the content of the polyol-based non-ionic surfactant in aqueous coating fluid is relative to total matter of aqueous coating fluid
Measure as more than 0.07 mass %, then the surface tension of aqueous coating fluid is greatly reduced, and the wetability of aqueous coating fluid becomes more preferable,
Therefore, it is possible to further improve the uniformity of coated film.If polyol-based non-ionic surfactant in aqueous coating fluid contains
Amount is below 1.0 mass % relative to the gross mass of aqueous coating fluid, then micelle forma-tion is inhibited in aqueous coating fluid, because
This can further improve the compactness of silicon dioxide granule when film is formed.
(water)
Aqueous coating fluid includes water.
It is used as the aqueous medium of aqueous coating fluid by using water, with a large amount of coating fluids using volatile organic solvent
Compare, can significantly mitigate the load to environment.
As the water for being used in aqueous coating fluid, preferably not comprising impurity, or the deionized water of its content is reduced as far as possible.
(other compositions)
Aqueous coating fluid is not in the range of the effect of the present invention is damaged, as needed, can also include except average one
Beyond secondary particle diameter is below the 8nm electronegative silicon dioxide granule in surface, polyol-based non-ionic surfactant and water
Other compositions.
As other compositions, hydrophilic organic solvent, water soluble polymer and water dispersed latex etc. can be enumerated.
- hydrophilic organic solvent-
Aqueous coating fluid in addition to water, can also include the hydrophilic organic solvent excellent with the compatibility of water.
Hydrophilic organic solvent is included by aqueous coating fluid, the surface tension of aqueous coating fluid further reduces, can be with
Carry out coating evenly.If also, hydrophilic organic solvent is low boiling point organic solvent, the drying with aqueous coating fluid
The advantages of becoming easy.
As hydrophilic organic solvent, there is no particular limitation, can enumerate methanol, ethanol, isopropanol, butanol, acetone,
Ethylene glycol and ethyl cellosolve etc..It is excellent as hydrophilic organic solvent from the viewpoint of easy availability, reduction carrying capacity of environment
Elect alcohol as, wherein, more preferably ethanol and isopropanol.
In the case where aqueous coating fluid is in addition to water also comprising hydrophilic organic solvent as aqueous medium, in water
The content of the water used in property coating fluid is preferably more than 30 mass % more preferably 40 matter relative to the gross mass of aqueous medium
Measure more than %.
Solid constituent amount in aqueous coating fluid is preferably the matter of 0.1 mass %~30 relative to the gross mass of aqueous coating fluid
Measure %, the mass % of more preferably 0.2 mass %~20 mass %, more preferably 0.5 mass %~10.In aqueous coating fluid
Solid constituent amount can be adjusted by the content of solvent particularly by the content of water.
(pH of aqueous coating fluid)
The pH of aqueous coating fluid is 8~12, preferably 9~11.
By the pH that is set to have gap with the isoelectric point (pH4~6) of silicon dioxide granule by the pH of aqueous coating fluid (8~
12), the cohesion of the silicon dioxide granule in aqueous coating fluid is inhibited, and the dispersiveness of silicon dioxide granule becomes good, recognizes
It can be improved for coating accuracy.Because the coating accuracy of aqueous coating fluid is improved, it is taken as that it is excellent especially to form antireflection
Different film.
If the pH of aqueous coating fluid is more than 8, the cohesion of the silicon dioxide granule in aqueous coating fluid is inhibited, because
This can form antireflection, scratch resistance and the excellent film of soil resistance.And it is possible to form the film of good surface state.
If the pH of aqueous coating fluid is more than 12, silicon dioxide granule is dissolved in aqueous coating fluid, therefore aqueous
The long-time stability of coating fluid suffer damage.If the pH of aqueous coating fluid is less than 12, silicon dioxide granule is not dissolved, therefore
Antireflection and the excellent film of soil resistance can be formed.
The isoelectric point of silicon dioxide granule is aobvious according to surface state of manufacture method, primary particle size and silicon dioxide granule etc.
Somewhat dipping and heaving is shown, in this case, the pH of the isoelectric point of silicon dioxide granule can also be coordinated to adjust aqueous coating fluid
PH.
The pH of aqueous coating fluid in this specification is to use pH instrument (models：HM-31, DKK-TOACORPORATION
Manufacture) value that is determined at 25 DEG C.
[film]
The film of the disclosure is manufactured by the manufacture method of the foregoing disclosure.Made by the manufacture method of the disclosure
The antireflection of the film made, scratch resistance and soil resistance are excellent.Hereinafter, the film manufactured by the manufacture method of the disclosure is shown
Preferred physical property.
(average reflectance changes delta R absolute value)
At least dried coated film can by the light in 400nm~1100nm wavelength that is defined by following formula (1) with
The absolute value of average reflectance changes delta R during 5 ° of incidence represents its antireflection property.
In addition, " at least dried coated film " as long as by the coated film of foregoing coated film drying process, " extremely
The coated film for passing through foregoing coated film firing process after coated film drying process is also included within few dried coated film ".
| average reflectance changes delta R |=| RFilm formed after base material average reflectance-RThe average reflectance of base material| formula (1)
Using barium sulfate blank as sample is referred to, the average reflectance for the base material for being formed without coated film is determined
(RThe average reflectance of base material) and base material with the coated film formed by aqueous coating fluid average reflectance (RFilm formed after base material average reflectance),
Thus, it is possible to obtain the average reflectance changes delta R in formula (1).
Reflectivity can be determined by using the spectrophotometer with integrating sphere.In the disclosure, as measure device
And use and pass through UV, visible light infrared spectrophotometer (model：UV3100PC, Shimadzu Corporation are manufactured), and make
The reflectivity in the light of 400nm~1100nm wavelength is determined with integrating sphere, using the value progress to the reflectivity in each wavelength
It is worth obtained from arithmetic average as average reflectance.
Represent that the numerical value of average reflectance changes delta R absolute value is higher, the antireflection of film is more excellent.
From the viewpoint of antireflection, at least dried coated film average reflectance changes delta R absolute value is preferred
For more than 2.0%, more preferably more than 2.5%.
(thickness)
From the viewpoint of antireflection, the thickness of the film of the disclosure is preferably more than 50nm and below 350nm, more preferably
For more than 100nm and below 300nm, more preferably more than 100nm below 250nm.
[aqueous coating fluid]
The aqueous coating fluid of the disclosure includes water, the electronegative silica in surface that average primary particle diameter is below 8nm
Particle, polyol-based non-ionic surfactant, and pH is 8~12.
Antireflection, scratch resistance and soil resistance can be manufactured by using the aqueous coating fluid of the disclosure excellent
Film.
The aqueous coating fluid of the disclosure is identical with the implication of the aqueous coating fluid in the manufacture method of the film of the foregoing disclosure,
Preferred embodiment is also identical.Omitted the description on common ground.
[layered product]
The layered product of the disclosure has the film manufactured by the manufacture method of the foregoing disclosure on base material.The disclosure
Layered product has the film manufactured by the manufacture method of the disclosure, therefore antireflection, scratch resistance and soil resistance are excellent.
There is no particular limitation for base material in the layered product of the disclosure.As base material, can enumerate glass, resin, metal,
The base material such as ceramics and their composite, these base materials can be used suitably.Wherein, from passing through foregoing public affairs
The manufacture method opened and from the viewpoint of adaptation between the film manufactured, be used as base material, preferably glass baseplate.
There is the layered product of film manufactured by the manufacture method of the disclosure on the glass substrate, due to antireflection,
Scratch resistance and soil resistance are excellent, therefore, it is possible to be adapted to be used in solar module, CCTV camera, lighting apparatus, mark
The purposes such as the diaphragm of label.
[solar module]
The solar module of the disclosure possesses the layered product of the foregoing disclosure.
The solar module of the disclosure is configured to, be arranged at sun light incident side antireflection,
The layered product of scratch resistance and the film of the excellent disclosure of soil resistance and the backboard used for solar batteries by representative of polyester film
Between, configuration is converted to the luminous energy of sunshine the solar cell device of electric energy.Layered product and polyester film of the disclosure etc.
By close by the encapsulant of representative of resins such as vinyl-vinyl acetate copolymers between backboard used for solar batteries
Envelope.
On solar module, solar battery cell etc., the part in addition to layered product and backboard, for example,
Being recorded in " photovoltaic power generation system constituent material " in detail, (China fir this Sakae one is supervized, Kogyo Chosakai Publishing
Co., Ltd., issues for 2008) in.In the solar module of the disclosure, preferably possesses the disclosure in sun light incident side
Layered product, the structure beyond the layered product of the disclosure is unimportant.
As the base material for being arranged at sun light incident side, transparent resins such as glass baseplate, acrylic resin etc. can be enumerated,
Preferably glass baseplate.
Solar cell device used in solar module as the disclosure, is not particularly limited.
Can be using various known solar cell devices in the solar module of the disclosure：Monocrystalline silicon, polysilicon, amorphous
Iii-v or the II-VI group chemical combination such as the silicon class such as silicon solar cell device, copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, gallium-arsenic
Thing semiconductor type solar cell device etc..
The solar module of the disclosure possesses has antireflection, scratch resistance and soil resistance good on the glass substrate
The layered product of good film, even if therefore use for a long time, can also suppress because the film on surface produces cut or attachment is polluted
Translucency caused by thing is reduced, because accompanying pollutant is easily removed by water such as rain, therefore can be maintained through long-time
Good generating efficiency.
Embodiment
Hereinafter, the present invention is more specifically illustrated by embodiment.The present invention, would not without departing from its purport
It is defined to following examples.
[embodiment 1]
(preparation of aqueous coating fluid 1)
In the water dispersion (trade name of silicon dioxide granule：NALCO (registration mark) 8699, nonporous silica silicon grain
Son, the average primary particle diameter of silicon dioxide granule：3nm, solid constituent：15 mass %, NALCO companies manufacture) 89.4 mass parts
In, add polyol-based non-ionic surfactant (trade name：TRITON (registration mark) BG-10, alkyl poly glucoside
Class surfactant, solid constituent：70 mass %, The Dow Chemical Company are manufactured) after 2.1 mass parts, with
Mode of the total amount as 1000 mass parts is further added deionized water and is stirred, and thus prepares aqueous coating fluid 1.In addition,
The content of silicon dioxide granule in aqueous coating fluid 1 is 90.2 mass % relative to the total solid content of aqueous coating fluid 1.
Use pH instrument (models：HM-31, DKK-TOA CORPORATION manufacture) determine aqueous coating fluid 1 pH (25
DEG C) result be 10.5.
(making of membrane sample 1)
Using rod coater, aqueous coating fluid 1 is coated with (coating weight：10mL/m2~20mL/m2) on glass baseplate and
Form coated film.Heated using baking oven at 150 DEG C of atmosphere temperature through 1 minute and dry the coated film.Then, using electricity
Stove was burnt till at 700 DEG C of atmosphere temperature through 3 minutes to dried coated film, thus produced membrane sample 1.
In addition, the final thickness that membrane sample 1 is fabricated to the coated film being formed on glass baseplate turns into 130nm.
[embodiment 2]
(preparation of aqueous coating fluid 2)
In the water dispersion (trade name of silicon dioxide granule：NALCO (registration mark) 8699, nonporous silica silicon grain
Son, the average primary particle diameter of silicon dioxide granule：3nm, solid constituent：15 mass %, NALCO companies manufacture) 89.4 mass parts
In, add polyol-based non-ionic surfactant (trade name：TRITON (registration mark) BG-10, alkyl poly glucoside
Class surfactant, solid constituent：70 mass %, The Dow Chemical Company are manufactured) after 1.1 mass parts, with
Mode of the total amount as 1000 mass parts is further added deionized water and is stirred, and thus prepares aqueous coating fluid 2.In addition,
The content of silicon dioxide granule in aqueous coating fluid 2 is 94.9 mass % relative to the total solid content of aqueous coating fluid 2.
Result by the pH (25 DEG C) that aqueous coating fluid 2 is determined with the identical method of aqueous coating fluid 1 is 10.5.
(making of membrane sample 2)
The aqueous coating fluid 1 used in the making of membrane sample 1 is changed to aqueous coating fluid 2, in addition, with film
The identical mode of sample 1 produces membrane sample 2.
[embodiment 3]
(preparation of aqueous coating fluid 3)
In the water dispersion (trade name of silicon dioxide granule：NALCO (registration mark) 8699, nonporous silica silicon grain
Son, the average primary particle diameter of silicon dioxide granule：3nm, solid constituent：15 mass %, NALCO companies manufacture) 89.4 mass parts
In, add polyol-based non-ionic surfactant (trade name：TRITON (registration mark) BG-10, alkyl poly glucoside
Class surfactant, solid constituent：70 mass %, The Dow Chemical Company are manufactured) after 6.3 mass parts, with
Mode of the total amount as 1000 mass parts is further added deionized water and is stirred, and thus prepares aqueous coating fluid 3.In addition,
The content of silicon dioxide granule in aqueous coating fluid 3 is 69.8 mass % relative to the total solid content of aqueous coating fluid 3.
Result by the pH (25 DEG C) that aqueous coating fluid 3 is determined with the identical method of aqueous coating fluid 1 is 10.5.
(making of membrane sample 3)
The aqueous coating fluid 1 used in the making of membrane sample 1 is changed to aqueous coating fluid 3, in addition, with film
The identical mode of sample 1 produces membrane sample 3.
[embodiment 4]
(preparation of aqueous coating fluid 4)
In the water dispersion (trade name of silicon dioxide granule：NALCO (registration mark) 8699, nonporous silica silicon grain
Son, the average primary particle diameter of silicon dioxide granule：3nm, solid constituent：15 mass %, NALCO companies manufacture) 89.4 mass parts
In, add polyol-based non-ionic surfactant (trade name：TRITON (registration mark) BG-10, alkyl poly glucoside
Class surfactant, solid constituent：70 mass %, The Dow Chemical Company are manufactured) after 10.5 mass parts, with
Mode of the total amount as 1000 mass parts is further added deionized water and is stirred, and thus prepares aqueous coating fluid 4.In addition,
The content of silicon dioxide granule in aqueous coating fluid 4 turns into 64.9 mass % relative to the total solid content of aqueous coating fluid 4.
Result by the pH (25 DEG C) that aqueous coating fluid 4 is determined with the identical method of aqueous coating fluid 1 is 10.5.
(making of membrane sample 4)
The aqueous coating fluid 1 used in the making of membrane sample 1 is changed to aqueous coating fluid 4, in addition, with film
The identical mode of sample 1 produces membrane sample 4.
[comparative example 1]
(preparation for comparing aqueous coating fluid 1)
In the water dispersion (trade name of silicon dioxide granule：NALCO (registration mark) 8699, nonporous silica silicon grain
Son, the average primary particle diameter of silicon dioxide granule：3nm, solid constituent：15 mass %, NALCO companies manufacture) 89.4 mass parts
In, add deionized water in the way of total amount turns into 1000 mass parts and be stirred, thus prepare and compare aqueous coating fluid 1.Separately
Outside, compare the content of the silicon dioxide granule in aqueous coating fluid 1 is relative to the total solid content for comparing aqueous coating fluid 1
100 mass %.
The result for being compared the pH (25 DEG C) of aqueous coating fluid 1 by being determined with the identical method of aqueous coating fluid 1 is
10.5。
(making for comparing membrane sample 1)
The aqueous coating fluid 1 used in the making of membrane sample 1 is changed to compare aqueous coating fluid 1, in addition, with
Produced with the identical mode of membrane sample 1 and compared membrane sample 1.
[embodiment 5]
(preparation of aqueous coating fluid 5)
In the water dispersion (trade name of silicon dioxide granule：SNOWTEX (registration mark) XS, nonporous silica silicon grain
Son, the average primary particle diameter of silicon dioxide granule：5nm, solid constituent：20 mass %, NISSAN CHEMICAL
INDUSTRIES, LTD. are manufactured) in 67.1 mass parts, add polyol-based non-ionic surfactant (trade name：TRITON
(registration mark) BG-10, alkyl poly glucoside class surfactant, solid constituent：70 mass %, The Dow Chemical
Company is manufactured) after 2.1 mass parts, in the way of total amount turns into 1000 mass parts further add deionized water and stirred
Mix, thus prepare aqueous coating fluid 5.In addition, the content of the silicon dioxide granule in aqueous coating fluid 5 is relative to aqueous coating fluid
5 total solid content is 90.2 mass %.
Result by the pH (25 DEG C) that aqueous coating fluid 5 is determined with the identical method of aqueous coating fluid 1 is 10.5.
(making of membrane sample 5)
The aqueous coating fluid 1 used in the making of membrane sample 1 is changed to aqueous coating fluid 5, in addition, with film
The identical mode of sample 1 produces membrane sample 5.
[embodiment 6]
(preparation of aqueous coating fluid 6)
In the water dispersion (trade name of silicon dioxide granule：NALCO (registration mark) 8699, nonporous silica silicon grain
Son, the average primary particle diameter of silicon dioxide granule：3nm, solid constituent：15 mass %, NALCO companies manufacture) 89.4 mass parts
In, add polyol-based non-ionic surfactant (trade name：TRITON (registration mark) BG-10, alkyl poly glucoside
Class surfactant, solid constituent：70 mass %, The Dow Chemical Company are manufactured) after 2.1 mass parts, with
Total amount turns into 1000 mass parts and pH turns into 8 mode, and further addition phosphoric acid and deionized water are adjusted, and thus prepare water
Property coating fluid 6.In addition, total solid content of the content of the silicon dioxide granule in aqueous coating fluid 6 relative to aqueous coating fluid 6
For 90.2 mass %.
(making of membrane sample 6)
The aqueous coating fluid 1 used in the making of membrane sample 1 is changed to aqueous coating fluid 6, in addition, with film
The identical mode of sample 1 produces membrane sample 6.
[comparative example 2]
(preparation for comparing aqueous coating fluid 2)
In the water dispersion (trade name of silicon dioxide granule：NALCO (registration mark) 8699, nonporous silica silicon grain
Son, the average primary particle diameter of silicon dioxide granule：3nm, solid constituent：15 mass %, NALCO companies manufacture) 89.4 mass parts
In, add polyol-based non-ionic surfactant (trade name：TRITON (registration mark) BG-10, alkyl poly glucoside
Class surfactant, solid constituent：70 mass %, The Dow Chemical Company are manufactured) after 2.1 mass parts, with
Total amount turns into 1000 mass parts and pH turns into 7 mode, and further addition phosphoric acid and deionized water are adjusted, and thus prepare ratio
Compared with aqueous coating fluid 2.In addition, comparing the content of the silicon dioxide granule in aqueous coating fluid 2 relative to comparing aqueous coating fluid 2
Total solid content be 89.9 mass %.
(making for comparing membrane sample 2)
The aqueous coating fluid 1 used in the making of membrane sample 1 is changed to compare aqueous coating fluid 2, in addition, with
Produced with the identical mode of membrane sample 1 and compared membrane sample 2.
[comparative example 3]
(preparation for comparing aqueous coating fluid 3)
In the water dispersion (trade name of silicon dioxide granule：NALCO (registration mark) 8699, nonporous silica silicon grain
Son, the average primary particle diameter of silicon dioxide granule：3nm, solid constituent：15 mass %, NALCO companies manufacture) 89.4 mass parts
In, add polyol-based non-ionic surfactant (trade name：TRITON (registration mark) BG-10, alkyl poly glucoside
Class surfactant, solid constituent：70 mass %, The Dow Chemical Company are manufactured) after 2.1 mass parts, with
Total amount turns into 1000 mass parts and pH turns into 13 mode, further addition 1mol/L sodium hydrate aqueous solution and deionized water
It is adjusted, thus prepares and compare aqueous coating fluid 3.In addition, comparing the content phase of the silicon dioxide granule in aqueous coating fluid 3
It is 89.9 mass % for the total solid content for comparing aqueous coating fluid 3.
(making for comparing membrane sample 3)
The aqueous coating fluid 1 used in the making of membrane sample 1 is changed to compare aqueous coating fluid 3, in addition, with
Produced with the identical mode of membrane sample 1 and compared membrane sample 3.
[comparative example 4]
(preparation for comparing aqueous coating fluid 4)
In the water dispersion (trade name of silicon dioxide granule：SNOWTEX (registration mark) AK, nonporous silica silicon grain
Son, the average primary particle diameter of silicon dioxide granule：13nm, solid constituent：19 mass %, NISSAN CHEMICAL
INDUSTRIES, LTD. are manufactured) in 84.9 mass parts, add polyol-based non-ionic surfactant (trade name：TRITON
(registration mark) BG-10, alkyl poly glucoside class surfactant, solid constituent：70 mass %, The Dow Chemical
Company is manufactured) after 2.1 mass parts, in the way of total amount turns into 1000 mass parts further add deionized water and stirred
Mix, thus prepare and compare aqueous coating fluid 4.In addition, compare the content of the silicon dioxide granule in aqueous coating fluid 4 relative to than
Total solid content compared with aqueous coating fluid 4 is 90.2 mass %.
The result for being compared the pH (25 DEG C) of aqueous coating fluid 4 by being determined with the identical method of aqueous coating fluid 1 is 5.
(making for comparing membrane sample 4)
The aqueous coating fluid 1 used in the making of membrane sample 1 is changed to compare aqueous coating fluid 4, in addition, with
Produced with the identical mode of membrane sample 1 and compared membrane sample 4.
[embodiment 7]
(preparation of aqueous coating fluid 7)
In the water dispersion (trade name of silicon dioxide granule：NALCO (registration mark) 8699, nonporous silica silicon grain
Son, the average primary particle diameter of silicon dioxide granule：3nm, solid constituent：15 mass %, NALCO companies manufacture) 89.4 mass parts
In, add polyol-based non-ionic surfactant (trade name：RHEODOL (registration mark) SP-P10, anhydrosorbitol
Fatty acid ester surfactant, solid constituent：100 mass %, Kao Corporation are manufactured) after 1.5 mass parts, with
Mode of the total amount as 1000 mass parts is further added deionized water and is stirred, and thus prepares aqueous coating fluid 7.In addition,
The content of silicon dioxide granule in aqueous coating fluid 7 is 89.9 mass % relative to the total solid content of aqueous coating fluid 7.
Result by the pH (25 DEG C) that aqueous coating fluid 7 is determined with the identical method of aqueous coating fluid 1 is 10.5.
(making of membrane sample 7)
The aqueous coating fluid 1 used in the making of membrane sample 1 is changed to aqueous coating fluid 7, in addition, with film
The identical mode of sample 1 produces membrane sample 7.
[embodiment 8]
(making of membrane sample 8)
Using rod coater, aqueous coating fluid 1 is coated with (coating weight：10mL/m2~20mL/m2) on glass baseplate and
Form coated film.Heated using baking oven at 150 DEG C of atmosphere temperature through 1 minute and dry the coated film, thus produced
Membrane sample 8.
In addition, the final thickness that membrane sample 8 is fabricated to the coated film being formed on glass baseplate turns into 130nm.
[comparative example 5]
(preparation for comparing aqueous coating fluid 5)
In the water dispersion (trade name of silicon dioxide granule：NALCO (registration mark) 8699, nonporous silica silicon grain
Son, the average primary particle diameter of silicon dioxide granule：3nm, solid constituent：15 mass %, NALCO companies manufacture) 89.4 mass parts
In, add Determination of Polyoxyethylene Non-ionic Surfactants (trade name：Newcole 2303-Y, polyoxygenated alkenes surface-active
Agent, solid constituent：100 mass %, Nippon Nyukazai Co., Ltd.s manufacture) after 1.5 mass parts, turned into total amount
The mode of 1000 mass parts is further added deionized water and is stirred, and thus prepares and compares aqueous coating fluid 5.In addition, comparing
The content of silicon dioxide granule in aqueous coating fluid 5 relative to compare aqueous coating fluid 5 total solid content be 90.2 matter
Measure %.
The result for being compared the pH (25 DEG C) of aqueous coating fluid 5 by being determined with the identical method of aqueous coating fluid 1 is
10.5。
(making for comparing membrane sample 5)
The aqueous coating fluid 1 used in the making of membrane sample 1 is changed to compare aqueous coating fluid 5, in addition, with
Produced with the identical mode of membrane sample 1 and compared membrane sample 5.
[comparative example 6]
(preparation for comparing aqueous coating fluid 6)
In the water dispersion (trade name of silicon dioxide granule：NALCO (registration mark) 8699, nonporous silica silicon grain
Son, the average primary particle diameter of silicon dioxide granule：3nm, solid constituent：15 mass %, NALCO companies manufacture) 89.4 mass parts
In, add anion surfactant (trade name：PELEX (registration mark) OT-P, sulfosuccinic acid Na class surface-actives
Agent, solid constituent：70 mass %, Kao Corporation are manufactured) after 10.5 mass parts, 1000 mass parts are turned into total amount
Mode further add deionized water and be stirred, thus prepare and compare aqueous coating fluid 6.In addition, comparing aqueous coating fluid 6
In silicon dioxide granule content relative to compare aqueous coating fluid 6 total solid content be 64.4 mass %.
The result for being compared the pH (25 DEG C) of aqueous coating fluid 6 by being determined with the identical method of aqueous coating fluid 1 is
10.5。
(making for comparing membrane sample 6)
The aqueous coating fluid 1 used in the making of membrane sample 1 is changed to compare aqueous coating fluid 6, in addition, with
Produced with the identical mode of membrane sample 1 and compared membrane sample 6.
[embodiment 9]
(preparation of aqueous coating fluid 8)
In the water dispersion (trade name of silicon dioxide granule：NALCO (registration mark) 1130, nonporous silica silicon grain
Son, the average primary particle diameter of silicon dioxide granule：8nm, solid constituent：30 mass %, NALCO companies manufacture) 44.7 mass parts
In, add polyol-based non-ionic surfactant (trade name：TRITON (registration mark) BG-10, alkyl poly glucoside
Class surfactant, solid constituent：70 mass %, The Dow Chemical Company are manufactured) after 2.1 mass parts, with
Mode of the total amount as 1000 mass parts is further added deionized water and is stirred, and thus prepares aqueous coating fluid 8.In addition,
The content of silicon dioxide granule in aqueous coating fluid 8 is 90.2 mass % relative to the total solid content of aqueous coating fluid 8.
Result by the pH (25 DEG C) that aqueous coating fluid 8 is determined with the identical method of aqueous coating fluid 1 is 10.5.
(making of membrane sample 9)
The aqueous coating fluid 1 used in the making of membrane sample 1 is changed to aqueous coating fluid 8, in addition, with film
The identical mode of sample 1 produces membrane sample 9.
[comparative example 7]
(preparation for comparing aqueous coating fluid 7)
In the water dispersion (trade name of silicon dioxide granule：NALCO (registration mark) 1030, nonporous silica silicon grain
Son, the average primary particle diameter of silicon dioxide granule：13nm, solid constituent：30 mass %, NALCO companies manufacture) 44.7 mass parts
In, add polyol-based non-ionic surfactant (trade name：TRITON (registration mark) BG-10, alkyl poly glucoside
Class surfactant, solid constituent：70 mass %, The Dow Chemical Company are manufactured) after 2.1 mass parts, with
Mode of the total amount as 1000 mass parts is further added deionized water and is stirred, and thus prepares and compares aqueous coating fluid 7.Separately
Outside, compare the content of the silicon dioxide granule in aqueous coating fluid 7 is relative to the total solid content for comparing aqueous coating fluid 7
89.9 quality %.
The result for being compared the pH (25 DEG C) of aqueous coating fluid 7 by being determined with the identical method of aqueous coating fluid 1 is
10.5。
(making for comparing membrane sample 7)
The aqueous coating fluid 1 used in the making of membrane sample 1 is changed to compare aqueous coating fluid 7, in addition, with
Produced with the identical mode of membrane sample 1 and compared membrane sample 7.
[embodiment 10]
(preparation of aqueous coating fluid 9)
In the water dispersion (trade name of silicon dioxide granule：NALCO (registration mark) 8699, nonporous silica silicon grain
Son, the average primary particle diameter of silicon dioxide granule：3nm, solid constituent：15 mass %, NALCO companies manufacture) 89.4 mass parts
In, add polyol-based non-ionic surfactant (trade name：RIKEMAL (registration mark) L-71-D, two glycerine fatty acids
Esters surface active agent, solid constituent：100 mass %, RIKEN VITAMIN CO., LTD. manufacture) after 1.5 mass parts, with
Mode of the total amount as 1000 mass parts is further added deionized water and is stirred, and thus prepares aqueous coating fluid 9.In addition,
The content of silicon dioxide granule in aqueous coating fluid 9 is 89.9 mass % relative to the total solid content of aqueous coating fluid 9.
Result by the pH (25 DEG C) that aqueous coating fluid 9 is determined with the identical method of aqueous coating fluid 1 is 10.5.
(making of membrane sample 10)
The aqueous coating fluid 1 used in the making of membrane sample 1 is changed to aqueous coating fluid 9, in addition, with film
The identical mode of sample 1 produces membrane sample 10.
[comparative example 8]
(preparation for comparing aqueous coating fluid 8)
In the water dispersion (trade name of silicon dioxide granule：SNOWTEX (registration mark) AK-XS, by based on calorize
The surface treatment of compound and the nonporous silica silicon particle of positively charged, the average primary particle diameter of silicon dioxide granule：5nm, solid
Composition：20 mass %, NISSAN CHEMICAL INDUSTRIES, LTD. manufacture) in 67.1 mass parts, addition polyol type is non-
Ionic surface active agent (trade name：TRITON (registration mark) BG-10, alkyl poly glucoside class surfactant, solid
Composition：70 mass %, The Dow Chemical Company are manufactured) after 2.1 mass parts, 1000 mass parts are turned into total amount
And pH turns into 10.5 mode, further addition 1mol/L sodium hydrate aqueous solution and deionized water is adjusted, and is thus made
It is standby to compare aqueous coating fluid 8.In addition, the content for comparing the silicon dioxide granule in aqueous coating fluid 8 is applied relative to relatively more aqueous
The total solid content of cloth liquid 8 is 89.9 mass %.
(making for comparing membrane sample 8)
The aqueous coating fluid 1 used in the making of membrane sample 1 is changed to compare aqueous coating fluid 8, in addition, with
Produced with the identical mode of membrane sample 1 and compared membrane sample 8.
[embodiment 11]
(making of membrane sample 11)
Using rod coater, aqueous coating fluid 1 is coated with (coating weight：10mL/m2~20mL/m2) on glass baseplate and
Form coated film.Heated using baking oven at 150 DEG C of atmosphere temperature through 1 minute and dry the coated film.Then, using electricity
Stove was burnt till at 450 DEG C of atmosphere temperature through 3 minutes to dried coated film, thus produced membrane sample 11.
In addition, the final thickness that membrane sample 11 is fabricated to the coated film being formed on glass baseplate turns into 130nm.
[embodiment 12]
(making of membrane sample 12)
Using rod coater, aqueous coating fluid 1 is coated with (coating weight：10mL/m2~20mL/m2) on glass baseplate and
Form coated film.Heated using baking oven at 150 DEG C of atmosphere temperature through 1 minute and dry the coated film.Then, using electricity
Stove was burnt till at 550 DEG C of atmosphere temperature through 3 minutes to dried coated film, thus produced membrane sample 12.
In addition, the final thickness that membrane sample 12 is fabricated to the coated film being formed on glass baseplate turns into 130nm.
[embodiment 13]
(making of membrane sample 13)
Using rod coater, aqueous coating fluid 1 is coated with (coating weight：10mL/m2~20mL/m2) on glass baseplate and
Form coated film.Heated using baking oven at 150 DEG C of atmosphere temperature through 1 minute and dry the coated film.Then, using electricity
Stove was burnt till at 800 DEG C of atmosphere temperature through 3 minutes to dried coated film, thus produced membrane sample 13.
In addition, the final thickness that membrane sample 13 is fabricated to the coated film being formed on glass baseplate turns into 130nm.
[embodiment 14]
(making of membrane sample 14)
Using rod coater, aqueous coating fluid 1 is coated with (coating weight：5mL/m2~10mL/m2) in shape on glass baseplate
Into coated film.Heated using baking oven at 150 DEG C of atmosphere temperature through 1 minute and dry the coated film.Then, using electric furnace
Dried coated film is burnt till through 3 minutes at 700 DEG C of atmosphere temperature, membrane sample 14 is thus produced.
In addition, the final thickness that membrane sample 14 is fabricated to the coated film being formed on glass baseplate turns into 75nm.
[embodiment 15]
(making of membrane sample 15)
Using rod coater, aqueous coating fluid 1 is coated with (coating weight：20mL/m2~30mL/m2) on glass baseplate and
Form coated film.Heated using baking oven at 150 DEG C of atmosphere temperature through 1 minute and dry the coated film.Then, using electricity
Stove was burnt till at 700 DEG C of atmosphere temperature through 3 minutes to dried coated film, thus produced membrane sample 15.
In addition, the final thickness that membrane sample 15 is fabricated to the coated film being formed on glass baseplate turns into 200nm.
[embodiment 16]
(making of membrane sample 16)
Using rod coater, aqueous coating fluid 1 is coated with (coating weight：35mL/m2~45mL/m2) on glass baseplate and
Form coated film.Heated using baking oven at 150 DEG C of atmosphere temperature through 1 minute and dry the coated film.Then, using electricity
Stove was burnt till at 700 DEG C of atmosphere temperature through 3 minutes to dried coated film, thus produced membrane sample 16.
In addition, the final thickness that membrane sample 16 is fabricated to the coated film being formed on glass baseplate turns into 300nm.
[embodiment 17]
(preparation of aqueous coating fluid 10)
In the water dispersion (trade name of silicon dioxide granule：NALCO (registration mark) 8699, nonporous silica silicon grain
Son, the average primary particle diameter of silicon dioxide granule：3nm, solid constituent：15 mass %, NALCO companies manufacture) 89.4 mass parts
In, add polyol-based non-ionic surfactant (trade name：TRITON (registration mark) BG-10, alkyl poly glucoside
Class surfactant, solid constituent：70 mass %, The Dow Chemical Company are manufactured) after 2.1 mass parts, with
Total amount turns into 1000 mass parts and pH turns into 10.9 mode, further addition 1mol/L sodium hydrate aqueous solution and deionization
Water is adjusted, and thus prepares aqueous coating fluid 10.In addition, the content of the silicon dioxide granule in aqueous coating fluid 10 relative to
The total solid content of aqueous coating fluid 10 is 89.9 mass %.
(making of membrane sample 17)
The aqueous coating fluid 1 used in the making of membrane sample 1 is changed to aqueous coating fluid 10, in addition, with
The identical mode of membrane sample 1 produces membrane sample 17.
[embodiment 18]
(preparation of aqueous coating fluid 11)
In the water dispersion (trade name of silicon dioxide granule：NALCO (registration mark) 8699, nonporous silica silicon grain
Son, the average primary particle diameter of silicon dioxide granule：3nm, solid constituent：15 mass %, NALCO companies manufacture) 89.4 mass parts
In, add polyol-based non-ionic surfactant (trade name：TRITON (registration mark) BG-10, alkyl poly glucoside
Class surfactant, solid constituent：70 mass %, The Dow Chemical Company are manufactured) after 2.1 mass parts, with
Total amount turns into 1000 mass parts and pH turns into 12 mode, further addition 1mol/L sodium hydrate aqueous solution and deionized water
It is adjusted, thus prepares aqueous coating fluid 11.In addition, the content of the silicon dioxide granule in aqueous coating fluid 11 is relative to water
Property coating fluid 11 total solid content be 89.9 mass %.
(making of membrane sample 18)
The aqueous coating fluid 1 used in the making of membrane sample 1 is changed to aqueous coating fluid 11, in addition, with
The identical mode of membrane sample 1 produces membrane sample 18.
[confirmation of the electriferous state of silicon dioxide granule]
The electriferous state of silicon dioxide granule to being included in above-mentioned resulting each aqueous coating fluid is confirmed.
In the state of aqueous coating fluid maintenance pH, dilution is appropriately using deionized water.On resulting aqueous coating
The dilution of liquid, uses Zeta potential measurement system (model：ELSZ-1, OTSUKA ELECTRONICSCo., LTD manufacture) survey
Determine Zeta potential, in the case where measurement result is bears, it is " negative " to be set to silicon dioxide granule powered, is positive in measurement result
In the case of, it is set to silicon dioxide granule powered for " just ".Show the result in table 1.
[evaluation of membrane sample]
On above-mentioned resulting each membrane sample, to antireflection (AR：Anti Reflection) it is property, scratch resistance, antifouling
Property and surface state are evaluated.Evaluation result is shown in table 1.
＜ antireflections (AR) property ＞
Pass through UV, visible light infrared spectrophotometer (model：UV3100PC, Shimadzu Corporation are manufactured), make
The reflectivity of the light of 400nm~1100nm wavelength of each membrane sample is determined with integrating sphere.
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.As obtained from by measure
The reflectivity of each wavelength in 400nm~1100nm wavelength calculates average reflectance, and is calculated according to following formula (1) relative to not
It is formed with the absolute value (| Δ R |) of the average reflectance change of the glass baseplate of film.In addition, | Δ R | represent that numerical value is higher, counnter attack
Penetrate (AR) property more excellent.
| average reflectance changes delta R |=| RFilm formed after base material average reflectance-RThe average reflectance of base material| formula (1)
＜ scratch resistances ＞
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 load, and 10 are carried out with speed 1000mm/min
After secondary reciprocating friction, by visual observation and light microscope (multiplying power：100 times) observation film surface, and according to following metewand
Scratch resistance is evaluated.In addition, being carried out under fluorescent light and under tungsten light source based on visual observation.Scratch resistance
[A], [B] and [C] in permissible range.
- metewand-
A：In visual and light microscope observation under visual, the tungsten light source under based on fluorescent lamp, on the surface of the film
Do not observe cut completely.
B：In visual observation under the visual and tungsten light source under based on fluorescent lamp, unconfirmed arrive is drawn on the surface of the film
Trace, but somewhat confirm in the observation based on light microscope cut.
C：It is unconfirmed on the surface of the film to arrive cut in the visual observation under based on fluorescent lamp, but based on tungsten light source
Under visual and light microscope observation in, cut is somewhat confirmed on the surface of the film.
D：In visual and light microscope observation under visual, the tungsten light source under based on fluorescent lamp, on the surface of the film
Linear scratches are confirmed, the quantity of the cut is 1~20.
E：In visual and light microscope observation under visual, the tungsten light source under based on fluorescent lamp, on the surface of the film
Linear scratches are confirmed, the quantity of cut is more than 21.
＜ soil resistances ＞
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 the natural sienna of attachment.Repeat after 10 operations, visually confirm
The attachment state of natural sienna, is evaluated soil resistance according to following metewands.In addition, [A] of soil resistance and
[B] is in permissible range.
- metewand-
A：In the unattached natural sienna in film surface, film surface water white transparency.
B：Somewhat adhere to natural sienna on the surface of the film, but film surface is almost colourless transparent.
C：Adhere to natural sienna in the whole face on film surface, confirm the transparency reduction on film surface by visual observation.
D：Adhere to natural sienna in the whole face on film surface, film surface is almost opaque.
＜ surface state ＞
Visually and light microscope (multiplying power：100 times), the surface of the membrane sample before being burnt till after seeing drying and burn till
The surface of membrane sample afterwards, surface state is have rated according to following metewands.In addition, in table 1, will note " before being burnt till after drying "
Carry as " not burning till ", will be recited as " burning till " " after burning till ".
- metewand-
A：Even if by visual observation and light microscope, also completely unconfirmed in the area of 30 centimeter squares on film surface arrive
The condensation product of silicon dioxide granule.
B：The condensation product unconfirmed to silicon dioxide granule in the area of the centimeter square of film surface 30 by visual observation, but
The condensation product of silicon dioxide granule is somewhat confirmed in the observation of light microscope.
C：By visual observation silicon dioxide granule is confirmed in being less than in 5% region for area of the centimeter square of film surface 30
Condensation product.
D：By visual observation two are confirmed in 5% region less than 30% of the area of the centimeter square of film surface 30
The condensation product of silicon oxide particle.
E：By visual observation titanium dioxide silicon grain is confirmed in more than 30% region of the area of the centimeter square of film surface 30
The condensation product of son.
As reference, the electron microscope of the surface state of [A] equivalent to metewand is shown respectively in Fig. 1 and Fig. 2
Photo (multiplying power：100 times) and surface state equivalent to [E] electron micrograph (multiplying power：100 times).
As shown in table 1, the antireflection of the membrane sample of embodiment, scratch resistance and soil resistance are excellent.Also, implementing
In the membrane sample of example, there is excellent surface state using membrane sample formed by aqueous coating fluid high pH.
The application advocate based on disclosed in Japanese patent application filed in 26 days December in 2014 2014-266486 all
Content by reference to and be applied 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 Japanese patent application and technical standard with by it is specific and with the situation identical degree recorded respectively, by reference to and
It is applied in this specification.
Claims (23)
1. a kind of manufacture method of film, it includes：
Coated film formation process, is coated with aqueous coating fluid on base material and forms coated film, and the aqueous coating fluid includes water, put down
Equal primary particle size is below the 8nm electronegative silicon dioxide granule in surface, polyol-based non-ionic surfactant, and pH is
8~12；And
Coated film drying process, the coated film for being coated with formation is dried.
2. the manufacture method of film according to claim 1, wherein,
The average primary particle diameter of the silicon dioxide granule is below 6nm.
3. the manufacture method of film according to claim 1 or 2, wherein,
The pH of the aqueous coating fluid is 9~11.
4. the manufacture method of film according to any one of claim 1 to 3, wherein,
Gross mass of the content of polyol-based non-ionic surfactant in the aqueous coating fluid relative to aqueous coating fluid
For the mass % of 0.07 mass %~1.0.
5. the manufacture method of film according to any one of claim 1 to 4, wherein,
The polyol-based non-ionic surfactant is with polyol type nonionic table of the cyclic polyether as hydrophilic radical
Face activating agent.
6. the manufacture method of film according to any one of claim 1 to 5, wherein,
The polyol-based non-ionic surfactant is alkyl poly glucoside class surfactant.
7. the manufacture method of film according to any one of claim 1 to 6, wherein,
After the coated film drying process, in addition to by dried coated film with more than 400 DEG C and less than 800 DEG C of temperature
Spend the coated film firing process burnt till.
8. the manufacture method of film according to claim 7, wherein,
Dried coated film is burnt till with the temperature of more than 500 DEG C and less than 800 DEG C in the coated film firing process.
9. the manufacture method of the film according to claim 7 or 8, wherein,
After the coated film drying process, the titanium dioxide silicon grain in the coated film before the coated film firing process
The content of son is the mass % of 64 mass %~95 relative to the total solid content of coated film.
10. the manufacture method of the film according to any one of claim 7 to 9, wherein,
The thickness of coated film after burning till is more than 50nm and below 350nm.
11. the manufacture method of film according to any one of claim 1 to 10, wherein,
The light in 400nm~1100nm wavelength that at least dried coated film is defined by following formula (1) is with flat during 5 ° of incidence
Equal reflectivity changes Δ R absolute value is more than 2.0%,
| average reflectance changes delta R |=| RFilm formed after base material average reflectance-RThe average reflectance of base material| formula (1).
12. the manufacture method of film according to claim 11, wherein,
The absolute value of the average reflectance changes delta R is more than 2.5%.
13. a kind of aqueous coating fluid, it includes water, the electronegative titanium dioxide silicon grain in surface that average primary particle diameter is below 8nm
Son, polyol-based non-ionic surfactant, and pH is 8~12.
14. aqueous coating fluid according to claim 13, wherein,
The average primary particle diameter of the silicon dioxide granule is below 6nm.
15. the aqueous coating fluid according to claim 13 or 14, wherein,
The pH of aqueous coating fluid is 9~11.
16. the aqueous coating fluid according to any one of claim 13 to 15, wherein,
The content of the silicon dioxide granule in aqueous coating fluid is 64 matter relative to the total solid content of aqueous coating fluid
Measure the mass % of %~95.
17. the aqueous coating fluid according to any one of claim 13 to 16, wherein,
The content of polyol-based non-ionic surfactant in aqueous coating fluid is relative to the gross mass of aqueous coating fluid
The mass % of 0.07 mass %~1.0.
18. the aqueous coating fluid according to any one of claim 13 to 17, wherein,
The polyol-based non-ionic surfactant is with polyol type nonionic table of the cyclic polyether as hydrophilic radical
Face activating agent.
19. the aqueous coating fluid according to any one of claim 13 to 18, wherein,
The polyol-based non-ionic surfactant is alkyl poly glucoside class surfactant.
20. a kind of film, it is manufactured by the manufacture method any one of claim 1 to 12.
21. a kind of layered product, it has the film described in claim 20 on base material.
22. layered product according to claim 21, wherein,
The base material is glass baseplate.
23. a kind of solar module, it possesses the layered product described in claim 21 or 22.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-266486 | 2014-12-26 | ||
| JP2014266486A JP2016123928A (en) | 2014-12-26 | 2014-12-26 | Aqueous coating liquid, film, and its manufacturing method, laminate, and solar cell module |
| PCT/JP2015/077626 WO2016103827A1 (en) | 2014-12-26 | 2015-09-29 | Aqueous coating liquid, film and method for producing same, laminate, and solar cell module |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106999982A true CN106999982A (en) | 2017-08-01 |
Family
ID=56149865
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580065615.5A Pending CN106999982A (en) | 2014-12-26 | 2015-09-29 | Aqueous coating fluid, film and its manufacture method, layered product and solar module |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2016123928A (en) |
| CN (1) | CN106999982A (en) |
| WO (1) | WO2016103827A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111269599A (en) * | 2020-03-19 | 2020-06-12 | 电子科技大学 | Ultraviolet radiation prevention structure for display device and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004099695A (en) * | 2002-09-06 | 2004-04-02 | Sekisui Film Kk | Antifogging agent applied by coating, and agricultural film |
| JP3806417B2 (en) * | 2003-05-29 | 2006-08-09 | 国立大学法人京都工芸繊維大学 | Aqueous coating composition and method for improving solvent resistance of coating film |
| JP4816223B2 (en) * | 2005-04-26 | 2011-11-16 | 住友化学株式会社 | Method for manufacturing antireflection laminate |
| JP5151109B2 (en) * | 2006-10-05 | 2013-02-27 | 住友化学株式会社 | LAMINATE MANUFACTURING METHOD AND SUBSTRATE PREVENTION METHOD |
| JP4698721B2 (en) * | 2008-10-17 | 2011-06-08 | 三菱電機株式会社 | Air conditioner and coating composition |
-
2014
- 2014-12-26 JP JP2014266486A patent/JP2016123928A/en not_active Abandoned
-
2015
- 2015-09-29 CN CN201580065615.5A patent/CN106999982A/en active Pending
- 2015-09-29 WO PCT/JP2015/077626 patent/WO2016103827A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111269599A (en) * | 2020-03-19 | 2020-06-12 | 电子科技大学 | Ultraviolet radiation prevention structure for display device and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2016103827A1 (en) | 2016-06-30 |
| JP2016123928A (en) | 2016-07-11 |
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