EP3867318A1 - Coating and coating formulation - Google Patents
Coating and coating formulationInfo
- Publication number
- EP3867318A1 EP3867318A1 EP19784086.1A EP19784086A EP3867318A1 EP 3867318 A1 EP3867318 A1 EP 3867318A1 EP 19784086 A EP19784086 A EP 19784086A EP 3867318 A1 EP3867318 A1 EP 3867318A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating
- substrate
- coating formulation
- inorganic oxide
- elongated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000008199 coating composition Substances 0.000 title claims abstract description 231
- 238000000576 coating method Methods 0.000 title claims description 209
- 239000000758 substrate Substances 0.000 claims abstract description 243
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 207
- 239000011148 porous material Substances 0.000 claims abstract description 73
- 239000002245 particle Substances 0.000 claims description 212
- 239000011248 coating agent Substances 0.000 claims description 192
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 156
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 81
- 239000003361 porogen Substances 0.000 claims description 76
- 229910052782 aluminium Inorganic materials 0.000 claims description 53
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 52
- 150000001875 compounds Chemical class 0.000 claims description 52
- 239000004411 aluminium Substances 0.000 claims description 50
- 239000011521 glass Substances 0.000 claims description 47
- 238000002834 transmittance Methods 0.000 claims description 35
- 239000011230 binding agent Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 33
- 239000011258 core-shell material Substances 0.000 claims description 31
- 239000002105 nanoparticle Substances 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 28
- 239000006117 anti-reflective coating Substances 0.000 claims description 26
- 239000002689 soil Substances 0.000 claims description 26
- 238000012360 testing method Methods 0.000 claims description 24
- 150000002894 organic compounds Chemical class 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 239000010410 layer Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- 229920006317 cationic polymer Polymers 0.000 claims description 12
- 238000003917 TEM image Methods 0.000 claims description 11
- 238000002485 combustion reaction Methods 0.000 claims description 10
- 239000006059 cover glass Substances 0.000 claims description 10
- 230000003667 anti-reflective effect Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000011247 coating layer Substances 0.000 abstract description 20
- 239000011162 core material Substances 0.000 description 39
- 239000011257 shell material Substances 0.000 description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 21
- 239000000377 silicon dioxide Substances 0.000 description 19
- 229910052681 coesite Inorganic materials 0.000 description 17
- 229910052906 cristobalite Inorganic materials 0.000 description 17
- 229910052682 stishovite Inorganic materials 0.000 description 17
- 229910052905 tridymite Inorganic materials 0.000 description 17
- 238000009835 boiling Methods 0.000 description 16
- 238000004140 cleaning Methods 0.000 description 15
- 239000002243 precursor Substances 0.000 description 15
- 238000004627 transmission electron microscopy Methods 0.000 description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 239000000523 sample Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000002296 dynamic light scattering Methods 0.000 description 10
- -1 for example AI2O3 Chemical class 0.000 description 10
- 238000009472 formulation Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229910044991 metal oxide Inorganic materials 0.000 description 10
- 150000004706 metal oxides Chemical class 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 125000002091 cationic group Chemical group 0.000 description 9
- 239000004816 latex Substances 0.000 description 9
- 229920000126 latex Polymers 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 239000000428 dust Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000000572 ellipsometry Methods 0.000 description 6
- 239000005329 float glass Substances 0.000 description 6
- 229920000620 organic polymer Polymers 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 230000001788 irregular Effects 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 239000012798 spherical particle Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 239000000443 aerosol Substances 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229920000359 diblock copolymer Polymers 0.000 description 3
- 238000001493 electron microscopy Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000010191 image analysis Methods 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 229920000307 polymer substrate Polymers 0.000 description 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000005341 toughened glass Substances 0.000 description 3
- 229920000428 triblock copolymer Polymers 0.000 description 3
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229920006318 anionic polymer Polymers 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- 244000089409 Erythrina poeppigiana Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002415 Pluronic P-123 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000009776 Rathbunia alamosensis Nutrition 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- WRMFBHHNOHZECA-UHFFFAOYSA-N butan-2-olate Chemical compound CCC(C)[O-] WRMFBHHNOHZECA-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229920003118 cationic copolymer Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000005345 chemically strengthened glass Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000007764 slot die coating Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002042 time-of-flight secondary ion mass spectrometry Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/006—Anti-reflective coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/69—Particle size larger than 1000 nm
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
-
- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/42—Coatings comprising at least one inhomogeneous layer consisting of particles only
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/73—Anti-reflective coatings with specific characteristics
- C03C2217/732—Anti-reflective coatings with specific characteristics made of a single layer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
- G02B2207/107—Porous materials, e.g. for reducing the refractive index
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
- G02B2207/109—Sols, gels, sol-gel materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the invention relates to an anti-reflective coating. More particularly, the invention relates to an anti-reflective coating showing anti-soiling properties as well as a coated substrate, a coating formulation and a solar module, as well as a method of improving anti-soiling properties of a coating.
- a coated substrate comprising a coating layer, said layer comprising inorganic oxide and pores is disclosed herein, the coating layer demonstrates improved anti-soiling properties.
- the coated substrate may for example be used in solar modules. Further a coating formulation and use of the coating formulation are disclosed.
- Anti-reflective (AR) coatings are coatings deposited on substrates, which require high transmission of light such as cover glasses for solar modules and green house glass, and said coatings are able to reduce the reflectivity of said substrates. Performance of solar modules tend to decrease over time amongst other reasons also due to soiling of the surface where light is transmitted through. In areas with high soiling rates, it was found that build-up of sand and dust particles provides a substantial contribution to the decreased performance.
- the improvement may for example be achieving of improved anti-soiling properties of the coating, or another feature of the invention.
- the object is achieved by a coating formulation according to the claims, embodiments and aspects as described herein.
- the object is achieved by a coating formulation as described herein.
- the objective is achieved by a method, a coated substrate, or a use according to the claims, embodiments and aspects as described herein,
- Figure 1 a schematically depicts an embodiment of an elongated particle used in the invention with an ellipsoidal shape (2D image of an prolate (elongated) spheroid), having a longer (which may also be referred to as major) axis having a length x1 perpendicular; a shorter (which may also be referred to as minor) axis perpendicular to the longer axis having a length x2; and an aspect ratio (x1/x2) of at least two.
- 2D image of an prolate (elongated) spheroid having a longer (which may also be referred to as major) axis having a length x1 perpendicular
- an aspect ratio (x1/x2) of at least two.
- Figure 1 b schematically depicts an embodiment of an elongated particle used in the invention with a rod-like shape, having
- a longer axis a having length x1 ; a shorter axis (smaller diameter) perpendicular to the longer axis having a length x2; and an aspect ratio (x1/x2) of at least two.
- Figure 1 c schematically depicts a spherical particle, having a first axis having a length x1 ;
- a second axis perpendicular to the first axis having a length x2; and an aspect ratio (x1/x2) of about 1.
- Figure 1 d schematically depicts an embodiment of an elongated particle used in the invention having an irregular shape, having
- a longer axis having a length x1 ; a shorter axis (smaller diameter, shortest dimension of the particle) perpendicular to the longer axis having a length x2 (the length of the longest straight line from one side of the particle to the other side of the particle); and an aspect ratio (x1/x2) of at least two.
- Fig. 2 shows optical properties of a comparative sample.
- Fig. 3 shows optical properties of a sample according to the invention.
- the invention relates to an improved coating.
- Such improved coating may be obtained by converting a coating formulation into a functional coating for example by heating.
- Coated substrates such as a cover glass of a solar module comprising an anti-reflective coating
- Coated substrates usually need cleaning at some point in time. In arid areas of the world cleaning involves among others time and costs and creates waste cleaning materials. There is therefore a need to reduce the cleaning frequency of coated substrates.
- This invention addresses the reduction of cleaning via improved anti-soiling properties of the coated substrate.
- the invention provides a coated substrate demonstrating improved anti-soiling properties.
- the invention provides a coating formulation demonstrating improved anti-soiling properties after application of such formulation on a substrate and converting the dried coating formulation into a coated substrate.
- the invention provides a solar module demonstrating improved anti-soiling properties.
- Improved anti-soiling properties may be demonstrated via reduced frequency of cleaning whilst having the same power output over a period of time e.g. 3 months.
- Improved anti-soiling properties may be demonstrated via an improved power output at the same frequency of cleaning over a period of time e.g. 3 months.
- Anti-soiling properties may be determined via measuring the transmittance of the anti- reflective coating on a transparent substrate by means of a transmission measurement using a spectrophotometer.
- the spectrophotometer can be any spectrophotometer which is suitable to analyse a coated substrate.
- a suitable spectrophotometer includes a Shimadzu UV2600 spectrophotometer.
- Another suitable spectrophotometer includes an Optosol Transpec VIS-NIR spectrophotometer.
- the improved anti-soiling properties may be demonstrated by an increased Anti-Soiling Ratio (ASR) as defined herein.
- Improved anti-soiling properties may be demonstrated by an increased substrate-coating anti-soiling ratio, ASR, as compared to a reference uncoated substrate.
- improved anti-soiling properties may be demonstrated by a substratecoating anti-soiling ratio, ASR, of at least 50%.
- the ASR is at least 55%.
- the ASR is at least 60%.
- the ASR is at least 65%.
- the ASR is at least 70%.
- the ASR is at least 75%.
- the ASR is at least 80%.
- the ASR is at least 90%.
- improved antisoiling properties may be demonstrated by an increased substrate-coating anti-reflective effect, ARE, as defined herein.
- Improved anti-soiling properties may be demonstrated by an increased ARE, as compared to a reference uncoated substrate.
- the ARE is at least 2%, in an aspect the ARE is at least 3%, in an aspect the ARE is at least 4%, in an aspect the ARE is at least 5%.
- the coating formulation according to the invention provides improved antisoiling properties.
- the coating formulation according to the invention provides improved antisoiling properties to a coating obtained from such formulation after curing i.e. by converting the coating formulation on a substrate into a coated substrate for example by heating, such as by heating above 400 degrees Celsius.
- the method according to the invention provides a coated substrate demonstrating improved anti-soiling properties.
- a coating formulation comprising
- elongated dense oxide particles with an aspect ratio of at least 2 and an average smaller diameter in the range of 3 to 20 nm; and ii. a porogen capable of forming pores with a diameter in the range of 10 to 120 nm,
- the coating formulation comprises of from 0.5 to 15 wt-% aluminium oxide equivalents of aluminium containing compound based on total ash rest after combustion at 600°C, 2 min in air.
- the average smaller diameter as referred to herein may be measured from at least one TEM image.
- the aspect ratio as referred to herein may be determined from at least one TEM image.
- the amount of aluminium oxide equivalents of aluminium containing compound in the ash rest of the coating formulation as referred to herein may be determined via ICP- MS.
- the coating formulation comprises at least 2 wt-%, at least 2,5 wt%, at least 3wt%, at least 3,5wt%, at least 4 wt%, at least 4,5 wt%, at least 5 wt%, at least 5,5 wt%, at least 6 wt%, at least 7 wt%, at least 8 wt%, at least 9 wt%, at least 10 wt %, based on inorganic oxide equivalents of elongated dense inorganic oxide particles with an aspect ratio of at least 2 and an average smaller diameter in the range of 3 to 20 nm.
- the coating formulation comprises at most 18 wt%, at most 17 wt %, at most 16 wt%, at most 15 wt%, at most 14 wt%, at most 13 wt%, at most 12 wt% at based on inorganic oxide equivalents of elongated dense inorganic oxide particles with an aspect ratio of at least 2 and an average smaller diameter in the range of 3 to 20 nm.
- the wt% of elongated dense inorganic oxide particles with an aspect ratio of at least 2 and an average smaller diameter in the range of 3 to 20 nm based on inorganic oxide equivalents may be calculated as follows.
- the coating formulation comprises at least 0.5 wt%, at least 1 wt%, at least 1 ,5 wt%, at least 2 wt%, at least 3 wt%, at least 4 wt%, at least 5 wt%, at least 6wt%, at least 10wt%, at least 12 wt % aluminium oxide equivalents of aluminium containing compound.
- the coating formulation comprises 15 wt% or less, 14 wt% or less, 13 wt% or less, 12 wt% or less, 1 1 wt% or less, 10 wt % or less , 9 wt% or less, 8 wt% or less aluminium oxide equivalents of aluminium containing compound.
- the coating formulation comprises from 1 to 15 wt% aluminium oxide equivalents of aluminium containing compound.
- the coating formulation comprises from 1 to 10 wt% aluminium oxide equivalents of aluminium containing compound.
- the coating formulation comprises from 2 to 10 wt% aluminium oxide equivalents of aluminium containing compound.
- the coating formulation comprises from 1 to 8 wt% aluminium oxide equivalents of aluminium containing compound.
- the coating formulation comprises from 1.5 to 8 wt% aluminium oxide equivalents of aluminium containing compound.
- the coating formulation comprises from 2 to 8 wt% aluminium oxide equivalents of aluminium containing compound.
- the objective is achieved by a method of preparing a coated substrate comprising the steps of: - providing a substrate;
- a method of preparing a coated substrate comprising the steps of:
- converting the substrate with dried coating formulation into a coated substrate comprising a coating layer on the first surface for example by heating, such as by heating above 400 degrees Celsius.
- a base coating as described herein forms at least a part of the first surface of the substrate. In an aspect a base coating as described herein forms the first surface of the substrate.
- the objective is achieved by a coated substrate obtainable by a method as described herein, including a method comprising the steps of
- the present invention further relates to a coated substrate comprising:
- the anti-reflective coating layer comprises pores with a diameter in the range of 10 to 120 nm, preferably 30 to 100 nm as measured using ellipsometry and / or electron microscopy;
- elongated dense inorganic oxide particles with an aspect ratio of at least 2, and a smaller diameter in the range of 3 to 20 nm;
- the objective is achieved by a use of a coating formulation comprising elongated inorganic oxide particles with an aspect ratio of at least 2 and a smaller diameter in the range of 3 to 20 nm for improving anti-soiling properties of a substrate, where the coating formulation comprising core-shell nanoparticle as porogen where the core comprises an organic compound, such as a polymer like a cationic polymer or an organic compound with a boiling point below 200°C, and the shell comprises an inorganic oxide, and from 0.5 to 15 wt-% aluminium oxide equivalents of aluminium containing compound.
- the objective is achieved by a use of a coating formulation comprising elongated dense inorganic oxide particles with an aspect ratio of at least 2 and a smaller diameter in the range of 3 to 20 nm for improving anti-soiling properties of a substrate, wherein the coating formulation comprises core-shell nanoparticles as porogen, wherein the core comprises an organic compound, such as a polymer or an organic compound with a boiling point below 200°C, the shell comprises a inorganic oxide; and the formulation comprises from 0.5 to 15 wt-% aluminium oxide equivalents of aluminium containing compound.
- the polymer may be a cationic polymer.
- the coating disclosed herein is a porous coating.
- the coating may be manufactured using a coating formulation comprising a binder and a porogen.
- the binder comprises inorganic binder particles, such as metaloxide particles, and or an inorganic oxide precursor.
- the porogen typically comprises an organic material that will decompose, burn, evaporate or be otherwise removed upon exposure to elevated temperature.
- the elevated temperature is 400 degrees Celcius or more, such as 550 degrees Celsius or more, such as 600 degrees Celsius or more.
- the organic material is an organic polymer.
- porogen comprises an organic material comprising an organic polymer such as an organic neutral, an organic cationic an organic anionic polymer, an polylectrolytes or a combination thereof.
- the porogen typically comprises an organic polymer core and an inorganic oxide shell around the core.
- the coating according to the disclosure comprises inorganic particles such as elongated inorganic dense oxide particles. It is noted that elongated inorganic dense oxide particles and elongated dense inorganic oxide particles are used interchangeably herein. It is noted that elongated inorganic dense oxide particles and elongated massive metal oxide particles are used interchangeably herein.
- the coating according to the invention comprises pores with a diameter in the range of less than 1 nm up to about 120 nm.
- the pores may be open pores, such as an opening along a boundary between two particles and optionally connecting to the surface of the coating, and/or the pores may be closed, such as a (closed) hollow particle. Pores that originate from a porogen are also referred to herein as porogen pores.lt is preferred that the coating comprises pores with a diameter of 10 to 120 nm, referred to as porogen pores.
- the pore diameter can be estimated by electron microscopy.
- porosimetry ellipsometry may be used to determine the pore size distribution.
- Porogen pores are preferably of substantially regular shape, such as spherical or ellipsoidal (with one or two long axes) pores.
- porogen pores are preferably of substantially regular shape, such as spherical or ellipsoidal (with one or two long axes) pores, but should not have an aspect ratio of more than 5 as this may negatively influence the mechanical properties of the coating.
- a hollow particle, such as an hollow inorganic oxide particle may be defined as a particle with an inorganic oxide shell with a hollow core.
- Porogen pores may be defined by a hollow inorganic oxide particle, such as for example hollow inorganic oxide particles and may originate from core-shell particles having an inorganic oxide (or inorganic oxide precursor) shell and an organic polymer based core, so that upon curing of the coating the polymer will be removed. Upon curing of the coating formulation the polymer will be decomposed/removed and the coating is formed.
- Porogen pores may be defined by a hollow inorganic oxide particle, such as for example hollow inorganic oxide particles and may originate from core-shell particles having an inorganic oxide (or inorganic oxide precursor) shell and a core material comprising an organic polymer and/or an organic compound, so that upon curing of the coating the core material will be removed.
- the core material Upon curing of the coating formulation the core material will be decomposed/removed such that a porous coating is formed.
- the pore typically originates from an organic porogen, that during conversion of the coating formulation into a functional coating typically will be decomposed, burned, evaporated or otherwise removed.
- a suitable curing temperature is at least 400 degrees Celsius. In an aspect a suitable curing temperature is at least 550, in an aspect at least degrees 600 Celsius.
- Pores may also be defined by a combination of inorganic binder particles and/or dense inorganic oxide particles. In this case, the pore typically originates from an organic porogen, such as a polymer particle or another porogen, that during conversion of the coating formulation into a functional coating typically will be decomposed, burned, evaporated or otherwise removed. Porogens include organic neutral, cationic and anionic polymers or polylectrolytes (see e.g. Fuji, M.; Takai, C.; Rivera Virtudazo, R. V.; Adv. Powder Tech., 2014, 25, 91 -100; Zhang, X. et ai, App. Mater. Interfaces, 2014, 6, 1415- 1423)
- the pore typically originates from an organic porogen, such as a polymer particle or another porogen, that during conversion of the coating formulation into a functional coating typically will be decomposed, burned, evaporated or otherwise removed. It should be observed that conversion does not encompass polymerization of organic (monomeric) compounds as the binder is an inorganic oxide based binder and the conversion therefore is of a sintering type conversion where organics are at least partially removed and metal oxide particles at least partially sinter together.
- an organic porogen such as a polymer particle or another porogen
- binder pores are therefore pores with a diameter of 1 to below 10 nm. Binder pores are typically not regular but extended pores in non-contacting regions between adjacent particles of binder, dense inorganic oxide particles and hollow nanoparticles (if present) and may form a network, which may or may not be in connection with the surface of the coating or with the porogen pores.
- the coating according to the invention is a porous coating.
- porous is herein meant that the coating has pores and a porosity of at least 2%.
- the maximum porosity depends on mechanical requirements of the coating layer and is typically 50% or less, preferably the porosity is less than 45% and more preferably the porosity is less than 40%.
- such coating layer has a porosity of 2 to 50%.
- a high porosity generally increases anti- reflective performance but may reduce mechanical strength of a coating.
- the porous anti-reflective coating layer has of porosity of 2% or more, 5% or more, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more.
- the porous anti-reflective coating layer has of porosity 50% or less, 45% or less, 40% or less. In an aspect the porous anti-reflective coating layer has of porosity of 25 to 40%. In an aspect the porous anti-reflective coating layer has of porosity of 30 to 40%.
- the porous anti-reflective coating layer may also be referred to herein as coating or anti-reflection coating.
- image analysis may suitably be performed on a SEM photo.
- the skilled person will be able to perform image analysis on a SEM photo of a cross section of the coating layer orthogonal to the substrate to determine that the amount of pores having a smallest dimension of at least 10 nm in the region of the AR coating closest to the surface of the substrate is smaller than the amount of pores having a smallest dimension of at least 10 nm in the region of the AR coating closer to the atmosphere.
- the skilled person may calculate the porosity from a measured refractive index (Rl). Knowing the Rl of a coating material without any pores, the skilled person can calculate how much air/pore volume is present in the coating layer.
- the coating material herein is the total inorganic oxide material after convert the coating formulation into a functional coating for example by heating.
- Total inorganic oxide material includes all inorganic oxide material in the coating e.g.
- porosity is determined by image analysis on a SEM photo of a cross section of the coating layer orthogonal to the substrate.
- the coating layer of the coated substrate has a porosity of 2 to 50%.
- the coating according to the invention also comprises elongated dense inorganic oxide particles with an aspect ratio of at least 2, and a smaller diameter in the range of 3 to 20 nm.
- the smaller diameter is in the range of 5 to 20 nm.
- elongated is meant that at least one of the dimensions of the particle is much longer, such as at least 2, 3, 4, 5, 8, 10, 15 or 20 times the length of another dimension of the particle. It is preferred that the length of the elongated dense inorganic oxide particle is less than 50 times the length of another dimension of the particle, such as at most, 50, 30, 25, 20 or 15 times the length of another dimension of the particle.
- the aspect ratio is calculated as the length of the longest straight line from one side of the particle to the other side of the particle (even though this may mean that the straight line may be outside the particle) divided by the shortest dimension of the particle transverse to the longest straight line anyway along the straight line.
- elongated dense inorganic oxide particles are IPA-ST-UP (Nissan Chemical) and Levasil CS15/175 (Akzo Nobel) and others are commercially available. Further examples include Levasil CS8-490 and Levasil CS15-150 (Akzo Nobel).
- the elongated particle has a diameter that is less than its length.
- the elongated dense particles comprises an elongated silica particle having a diameter of from 1 to 30 nm and a length of from 10 to 200 nm.
- the elongated dense particle comprises an elongated silica particle having a diameter from 9 to 15 nm and a length of length from 40 to 100 nm.
- IPA-ST-UP (Nissan Chemical) is an example of an elongated silica particle having a diameter of from 9 to 15 nm, and a length of length: 40-100 nm.
- the elongated dense particles is an elongated silica particle having a diameter of from 1 to 30 nm and a length of from 10 to 200 nm.
- the elongated dense particle is an elongated silica particle having a diameter from 9 to 15 nm and a length of length from 40 to 100 nm.
- IPA-ST-UP (Nissan Chemical) is an example of an elongated silica particle having a diameter of from 9 to 15 nm, and a length of length: 40-100 nm.
- IPA-ST-UP herein refers to ORGANOSILICASOLTM IPA-ST-UP.
- the elongated particle has an aspect ratio of at least two and may, without being limited thereto, have an ellipsoidal, a rod-like or an irregular shape.
- the elongated particle as used in the invention has a longer axis (which may also be referred to as major) having length x1 ; and a shorter axis perpendicular to the longer axis (which may also be referred to as minor) having a length x2; and an aspect ratio (x1/x2) of at least two.
- the aspect ratio is calculated by dividing the length of the longest axis by the smaller axis.
- the longest axis may also be referred to as major axis.
- the smaller axis may also be referred to as the minor axis, the smaller diameter or the shortest dimension of the particle.
- the outside surface of the particle is used.
- dense By dense is meant that the inorganic oxide particle has low or no porosity, such as a porosity of less than 5 vol-% or no porosity.
- the elongated dense inorganic oxide particle has a porosity of 0.5 - 5 vol-%, in an aspect 1 -4 vol-%, in an aspect 1-3 vol-% porosity.
- porogen an entity capable of forming pores with a diameter of 10 to 120 nm, preferably 30 to 100 nm, in the final coating may for example be hollow particle; a core-shell particle with a core with a boiling point below the curing temperature of the coating formulation or a core, which is combustable or depolymerizable below the curing temperature; a particle, which is combustable or depolymerizable below the curing temperature. Porogen may also be referred to as pore forming agent.
- a core with a boiling point below the curing temperature boiling point has a decomposition temperature of below the curing temperature.
- a core which is combustable or depolymerizable below the curing temperature is a core that is decomposed or depolymerized, or a combiantion thereof, during curing, i.e. at a temperature which is below the curing temparature. As a result the core is removed and a pore is formed.
- porogen or pore forming agent
- the porogen may be a polymer particle e.g. a polystyrene particle, Pluronic P123 and / or a PMMA particle.
- the porogen may for example be hollow particle.
- the porogen may for example be a hollow silica particle.
- the porogen may for example be a core-shell particle with a core having a boiling point below the curing temperature of the coating formulation.
- the porogen may be a core-shell particle with a core that is combustable or
- a core having a boiling point below the curing temperature comprises a material having boiling point of below the curing temperature.
- oxide equivalents of inorganics is herein meant the metal oxides including silicon oxide irrespective of the actual compound that the inorganic species is present in so for example tetraethoxysilane would count as S1O 2 irrespective if the species present is tetraethoxysilane, partially hydrolysed tetraethoxysilane or S1O 2 . i.e.
- oxide equivalents of inorganics is herein meant the equivalent amount of metal oxides including silicon oxide that can be formed from the actual compound or inorganic oxide precursor used. So for example a certain amount of tetraethoxysilane would be expressed as S1O 2 equivalent irrespective if the species present is tetraethoxysilane, partially hydrolysed
- the wt% Aluminum oxide equivalents are referring to the wt% as compared to the total amount of inorganic oxide equivalents in the coating formulation. It may also be phrased as wherein wt% AI203 is expressed as
- the alumina precursor may include
- Al(lll) complexes such as halogen-based salts of Al(lll) in the form of AIX3 where X can be F, Cl, Br, I and their hydrate form;
- Al(lll) inorganic salts such as Al(lll) nitrates, nitrites, sulfites, sulfates, phosphates, chlorates, perchlorates, carbonates and their hydrate form;
- the alumina precursor may include any of AI(isopropoxide)3, Al(sec- butoxide)3, AI(N03)3, AICI3 or a combination thereof.
- TEOS tetraethoxysilane
- TMOS tetramethoxysilane
- the inorganic oxide equivalents of the coating formulation are based on total ash rest after combustion at 600°C, 2 min in air.
- total ash rest after combustion at 600°C, 2 min in air is the total residual solid material after combustion at 600°C, 2 min in air.
- TEOS tetraethyl orthosilicate
- the amount of inorganic oxide equivalents is calculated as follows:
- the elongated particles used in the examples are considered to be pure Si02. So 1 gram elongated particles, is equivalent to 1 g inorganic oxide ( here 1 gram Si02).
- the porogen account for a significant part of the total amount of inorganic oxide in the coating formulation.
- the porogen accounts for 10 to 75 wt-% of the total amount of inorganic oxide in the coating formulation, and more preferably the porogen accounts for 20 to 50 wt-% of the total amount of inorganic oxide in the coating formulation. This may for example be the situation when the porogen is a core shell particle or a hollow particle.
- the inorganic oxide may be any oxide known from glass coatings.
- the inorganic oxide may be any known from glass coatings including metal oxides such as for example AI 2 O 3 , S1O 2 , T1O 2 , ZrC>2, oxides of lanthanides and mixtures (including mixed oxides) thereof.
- the inorganic oxide may be any known from glass coatings including metal oxides, compounds and mixtures comprising for example AI 2 O 3 , S1O 2 and optionally one or more of of Li20, BeO, BaO, MgO, K20, CaO, MnO, NiO SrO, FeO, Fe203, CuO, Cu20, CoO, ZnO, PbO, Ge02, Sn02, Sb203, Bi203.
- the inorganic oxide comprises AI 2 O 3 , S1O 2 , T1O 2 , ZrC>2 and/or combinations thereof.
- the inorganic oxide contains silica, preferably the inorganic oxide contains at least 50 wt-% silica and more preferably the inorganic oxide is at least 90 wt-% silica, such as the inorganic oxide consisting of silica.
- the coated substrate according to the invention may for example be prepared by a method comprising the steps of providing a substrate; providing a coating formulation according to the invention; apply the coating formulation on the substrate; drying the coating formulation on the substrate; and converting the coating formulation on the substrate into a coated substrate.
- the conversion does not involve polymerization of an organic polymer but rather a consolidation of the binder and/or conversion of the porogen into a pore in the coating. This may be by heating for example combined with a tempering process of a glass substrate, but may alternatively involve evaporation of solvent in a solvent templated particle, which may take place at a much lower temperature.
- the core comprises a solvent
- conversion of the porogen into a pore may involve evaporation of solvent, for example at temperature below 250 °C.
- the solvent may have a boiling point of at most 250 °C, or at most 200, 175 or 150 °C.
- a substrate comprising an applied coating formulation according to the invention is converted into a coated substrate comprising a coating layer on the first surface by exposing the applied coating formulation to a temperature of below 250°C. In an aspect by exposing the applied coating formulation to a temperature of below 200, below 175 or below 150 °C.
- An anti-reflective coating comprising IPA-ST-UP particles (elongated particles) and inorganic binder is disclosed in W02007/093341.
- W02007/093341 does not indicate any relevance to anti-soiling properties and does not disclose presence of pores having a diameter of 10-120 nm in the coating, and particularly not pores of a diameter of 30-100 nm.
- the coating When the coating is applied to a substrate, such as a glass sheet, the coating will have an inner surface facing towards the substrate and an outer surface facing away from the substrate.
- the elongated dense inorganic oxide particles are not distributed homogeneously in the coating.
- the mass ratio of inorganic oxide originating from elongated dense inorganic oxide particles to total inorganic oxide of the coating is higher in or near the outer surface of the coating.
- outer surface refers to the surface of the coating away from the substrate, which surface typically is exposed to the atmosphere.
- the distribution may for example be determined by STEM-EDX or by depth profiling.
- the distribution of elongated dense inorganic oxide particles in a coating may for example be determined by STEM-EDX or by depth profiling. This is particularly advantageous when the chemical composition of the dense inorganic oxide particles and the overall formulation is not the same.
- the mass ratio of inorganic oxide originating from elongated dense inorganic oxide particles to total inorganic oxide of the coating is higher in or near the outer surface of the coating as compared to a reference coating.
- a suitable reference coating may be a coating without elongated dense inorganic oxide particles.
- the ratio is higher in the 20 nm of the coating closest to the outer surface than the average mass ratio of the inorganic oxide originating from elongated dense inorganic oxide particles to total inorganic oxide of the coating.
- the ratio of inorganic oxide originating from elongated dense inorganic oxide particles to total inorganic oxide of the coating is at least 50% higher in the 20 nm of the coating closest to the outer surface compared to the average ratio of the inorganic oxide originating from elongated dense inorganic oxide particles to total inorganic oxide of the coating.
- the ratio is higher in the 20 nm of the coating closest to the outer surface that the average mass ratio of the inorganic oxide originating from elongated dense inorganic oxide particles to total inorganic oxide of the coating.
- the ratio of inorganic oxide originating from elongated dense inorganic oxide particles to total inorganic oxide of the coating is at least 50% higher in the 20 nm of the coating closest to the outer surface that the average ratio of the inorganic oxide originating from elongated dense inorganic oxide particles to total inorganic oxide of the coating, and more preferably the ratio of inorganic oxide originating from elongated dense inorganic oxide particles to total inorganic oxide of the coating is at least twice as high in the 20 nm of the coating closest to the outer surface that the average ratio of the inorganic oxide originating from elongated dense inorganic oxide particles to total inorganic oxide of the coating.
- the coated substrate according to the invention demonstrates the mass ratio of inorganic oxide originating from the elongated dense inorganic oxide particles to total inorganic oxide of the coating being higher in a 20 nm thick top layer of the coating closest to the outer surface of the coated substrate than the average mass ratio of the inorganic oxide originating from dense inorganic oxide particles to total inorganic oxide of the coating.
- the mass ratio of inorganic oxide originating from the dense inorganic oxide particles to total inorganic oxide of the coating is at least 50% higher in the top layer of the coating than the average mass ratio of the inorganic oxide originating from elongated dense inorganic oxide particles to total inorganic oxide of the coating.
- the mass ratio of inorganic oxide originating from the elongated dense inorganic oxide particles to total inorganic oxide of the coating is at least twice as high in the top layer the coating than the average mass ratio of the inorganic oxide originating from dense inorganic oxide particles to total inorganic oxide of the coating.
- the coating according to the invention shows improved anti-soiling properties.
- the improved anti-soiling properties may be demonstrated by an increased Anti-Soiling Ratio (ASR) as defined by: where“T” is the average transmittance from 380-1 100 nm measured by a
- ASR Anti-Soiling Ratio
- Substrate refer to substrate without coating
- Coating refers to the substrate with double sided coating.
- “0” refer to the measured transmittance before the soil test and“soil” refers to transmittance after soil test.
- From 380-1 100 nm herein means in the wavelength region from 380 nm to 1 100 nm including 1 100 nm.
- “T” is the average transmittance from 380-1 100 nm measured by a Shimadzu UV2600
- the coated substrate demonstrates an ASR of at least 50%. In an aspect the coated substrate demonstrates an ASR of at least 75%. In an aspect the coated substrate demonstrates an ASR of at least 80%. In an aspect the coated substrate demonstrates an ASR of at least 90%.
- the soil test is conducted as described in the experimental part.
- a soil test may include: a) Providing a substrate with a surface to be tested;
- Tsubstrate.o the average transmittance from 380-1 100 nm of the uncoated glass surface (substrate without coating) before soil test
- T S ubstrat e ,soii the average transmittance from 380-1 100 nm of the uncoated glass surface after soil test
- Tc oating .o the average transmittance from 380-1 100 nm of the coated glass surface (coating with double sides coating) before soil test
- Tc oating.soii the average transmittance from 380-1 100 nm of the coated glass surface after soil test.
- Tcoating.o may also be referred to herein as Tcoated substrate, 0 or T coated substrate with Al,0 O G T coated substrate without Al,0.
- Tcoating.soii may 3lS0 be referred to herein as Tcoated substrate, soil or Tcoa:o:: S ..::s:'a:e w : " A so or Tcoa:e:: substrate without Al.soil.
- step e) of the soil test Oscillating may be done by 300 cycles at a speed of 100 cycles per minute; one cycle being defined as a full revolution of the circular drive disk: one completed back-and-forth movement of the tray of a Taber Oscillating table.
- step f) of the soil test removing excess dust may be done by manually gently tapping a thin edge of the substrate (the side of the glass plate) on a hard surface, such as a table top.
- Removing excess dust may be followed by cleaning the back side (the front side being the surface to receive the incident light in the spectrophotometer) of the soiled substrate (soiled glass plate) by gently wiping the back side surface with a soft cloth;
- cleaning comprises: cleaning with deionized water and a soft cloth, rinsing with laboratory grade ethanol and leaving to dry overnight.
- Preferably cleaning is done at a relative humidity of below 40%.
- Soil test and soiling test are used interchangeably herein.
- the average transmittance from 380-1 100 nm means the average transmittance value in the wavelength range of 380 to 1 100 nm.
- the transmittance is measured using an Optosol Transpec VIS-NIR spectrophotometer.
- the transmittance is measured using an Shimadzu UV2600
- step d) and e) above is performed using a Taber Oscillating Abrasion Tester (such as model 6160).
- ASR indicates how well the coating improves the anti-soiling properties of the substrate.
- An ASR of 50% hence means that the coating only loses half the transmittance compared to the transmittance loss of the naked substrate.
- a naked substrate herein is a substrate without a coating layer, e.g. an uncoated piece of glass.
- the substrate-coating ASR of the coating is at least 75%, more preferably the substrate-coating ASR is at least 80%, and most preferably the substrate-coating ASR is at least 90%.
- ASR cannot be higher than 100% since this would mean that the coating is better after soiling, so the ASR should be maximum 100%.
- the invention provides a coated substrate obtainable by the method of preparing a coated substrate according to the invention, demonstrating improved antisoiling properties.
- the invention provides a coated substrate comprising:
- the anti-reflective coating comprises
- elongated dense inorganic oxide particles with an aspect ratio of at least 2, and a smaller diameter in the range of 3 to 20 nm;
- aluminium oxide equivalents of aluminium containing compound preferably 0.5 to 30 wt-% aluminium oxide equivalents of aluminium containing compound.
- the wt-% aluminium oxide equivalents of aluminium containing compound in the antireflective coating may be determined using STEM EDX. Alternatively it may be determined using ToF-SIMS.
- the coating formulation comprises at least 0.5 wt%, at least 1 wt%, at least 1 ,5 wt%, at least 2 wt%, at least 3 wt%, at least 4 wt%, at least 5 wt%, at least 6wt%, at least 10wt%, at least 12 wt % aluminium oxide equivalents of aluminium containing compound.
- the coating formulation comprises 15 wt% or less, 14 wt% or less, 13 wt% or less, 12 wt% or less, 1 1 wt% or less, 10 wt % or less , 9 wt% or less, 8 wt% or less aluminium oxide equivalents of aluminium containing compound.
- the porous anti-reflective coating layer may also be referred to herein as coating.
- the substrate is a solid material, such as a polymer sheet or a glass member.
- the substrate may include quartz or polymer foil, such as glass foil.
- polymer substrates are plastic foils and polymers based on one or more of the polymers selected from Polyethylene terephthalate (PET), Polymethyl methacrylate (PMMA), Polyethylene naphthalate (PEN), polycarbonate (PC).
- PET Polyethylene terephthalate
- PMMA Polymethyl methacrylate
- PEN Polyethylene naphthalate
- PC polycarbonate
- a further example of a polymer substrate includes polyimide (PI).
- PI polyimide
- Polymer substrates are advantageous for flexible solar cells.
- the substrate is transparent.
- the substrate is having an average transmission of at least 80% in the range of 380 -1 100 nm.
- the substrate is a glass member being selected from the group of float glass, chemically strengthened float glass, borosilicate glass, structured glass, tempered glass and thin flexible glass having thickness in the range of for example 20 to 250 pm such as 50 to 100 pm as well as substrates comprising a glass member, such as a partially or fully assembled solar module and an assembly comprising a glass member.
- the glass member may be SM glass or MM glass.
- a commercially available MM glass includes Interfloat GMB SINA 3.2mm solar glass for photovoltaic applications.
- the coated substrate is a cover glass for a solar module.
- the invention further relates to a solar module comprising a coated substrate as described herein.
- Solar modules are modules typically comprise a glass member forming at least a part of the first surface of the substrate and at least one member selected from the group consisting of thin film transparent conductive and/or semiconductor layers, a back sheet, an encapsulant, solar cells, an electrical conducting film, wiring, controller box and a frame.
- the glass member may be selected from the group of float glass, chemically strengthened float glass, borosilicate glass, structured glass, tempered glass and thin flexible glass having thickness in the range of for example 20 to 250 pm such as 50 to 100 pm.
- Preferred substrates for the method according to the invention are hence tempered glass, chemically strengthened glass and substrates comprising temperature sensitive components, such as partially or fully assembled solar cell modules.
- the substrate comprises a transparent solid sheet member with a base coating on a first side of the sheet member so the base coating forms at least a part of the first surface of the substrate, to be coated with the single non-laminated layer coating layer.
- the base coating is selected from the group of barrier coatings, such as sodium barrier coatings, and anti- reflective coatings.
- the coated substrate according to the invention comprises a transparent solid sheet member, and a base coating layer interposed between the first surface and the coating layer on the first coating, preferably the base coating is selected from the group of barrier coatings and anti-reflective coatings.
- the substrate is transparent solid sheet member with a base coating on a first side of the sheet member so the base coating forms at least a part of the first surface of the substrate.
- the substrate is transparent solid sheet member with a base coating on a first side of the sheet member so the base coating forms the first surface of the substrate.
- the coating according to the invention is preferably an anti-reflective coating.
- the coated substrate demonstrates an ARE of at least 2%, at least 3%, at least 4%, at least 5%.
- coated substrate according to the invention demonstrates a substrate coating anti-reflective effect, ARE, with
- T is the is the average transmittance in the wavelength range from 380-1 100 nm
- Substrate refers to substrate without coating
- Coated substrate refers to the substrate with double sided coating
- 0 refers to before soil test.
- T is the average transmittance from 380-1 100 nm measured by a Shimadzu UV2600 spectrophotometer.
- T is the average transmittance from 380-1 100 nm measured by an Optosol Transpec VIS-NIR spectrophotometer.
- the coating according to the invention is particularly suitable for lowering the reflectivity of a substrate for example any type of glass substrate, hence being used as an anti-reflective coating.
- Another aspect of the invention relates to a coating formulation
- a coating formulation comprising a porogen capable of forming pores with a diameter of 10-120 nm, elongated dense inorganic oxide particles with an aspect ratio of at least 2 and a smaller diameter in the range of 3 to 20 nm, an inorganic binder, a solvent and from 0.5 to 15 wt-% aluminium oxide equivalents of aluminium containing compound.
- Aluminium and aluminum are used interchangeably herein.
- the aluminium oxide equivalents of aluminium containing compound are based on total ash rest after combustion at 600°C, 2 min in air.
- the aluminium may be provided for example as metal oxide powder, but more preferably as an organic or inorganic salt optionally in solution or suspension.
- the coating formulation comprises from 1.0 to 15 wt-% aluminium oxide equivalents of aluminium containing compound as it was found that the stability in the sense of shelf life was best for aluminium concentrations in this range.
- Stability refers to the stability of the coating formulation.
- the stability of the coating formulation may be assessed by looking at the homogeneity of the coating formulation.
- An inhomogeneous coating formulation indicates a low stability and low shelf life.
- the inhomogeneity of the formulation can be directly observed by the presence of sediments or gellation in the liquid formulation or can be measured by DLS (Dynamic Light Scattering) via the growth or aggregation of colloidal particles in the suspension over time.
- DLS Dynamic Light Scattering
- the coating formulation comprises from 2 to 10 wt-% aluminium oxide equivalents of aluminium containing compound as it was found that that provides very good anti-soiling properties.
- the coating formulation according to the invention comprises
- a porogen capable of forming pores with a diameter in the range of 10 to 120 nm
- the coating formulation comprises from 0.5 to 15 wt-% aluminium oxide equivalents of aluminium containing compound based on total ash rest after combustion at 600°C, 2 min in air.
- the porogen may for example be hollow inorganic oxide particles, or coreshell particles having an inorganic oxide (or inorganic oxide precursor) shell and a core comprising an organic compound, such as a cationic polymer or an organic compound with a boiling point below 200°C.
- the porogen may also be an organic porogen, such as organic nanoparticle like for example an organic polymeric nanoparticle or another porogen, that during conversion of the coating formulation into a functional coating typically will be decomposed, burned, evaporated or otherwise removed.
- organic nanoparticle is herein meant a particle comprising one or more organic molecules and having a size in the range of 50 to 150nm. Examples of organic molecules are polymers, such as acrylic polymers and latexes; and oligomers. The elongated dense inorganic oxide particle is discussed above.
- the porogen comprises
- the core comprises an organic compound, such as a polymer or an organic compound with a boiling point below 200°C, and the shell comprises an inorganic oxide;
- the porogen comprises core-shell nanoparticles wherein the core comprises an organic compound, such as a polymer or an organic compound with a boiling point below 200°C, and the shell comprises an inorganic oxide.
- core-shell nanoparticles herein comprise
- core-shell nanoparticles herein comprise
- the core material comprises polymeric material (for example, homopolymers, random co-polymers, block-copolymers etc.).
- the polymer is selected from polyesters, polyamides, polyurethanes, polystyrenes, poly(meth)acrylates, copolymers and combinations thereof.
- the core comprises a poly(meth)acrylate.
- polymer is selected from latexes, diblock-copolymers, triblock copolymers, and combinations thereof.
- the polymer is a cationic copolymer comprising partially or fully quaternized amine functional vinyl monomer
- the core-shell nanoparticles herein comprise:
- core-shell nanoparticles herein comprise
- latex refers to stabilized suspension of
- the suspension is an emulsion.
- the latex is cationic.
- the cationic group may be incorporated in to the polymer or may be added in any other form such as, for example, by the addition of a cationic surfactant.
- the cationic groups are at least partially bound to the polymer. In an aspect the cationic groups are incorporated into the polymer during polymerisation.
- the latex comprises polymer and cationic surfactant.
- the surfactant comprises ammonium surfactant.
- Any suitable polymer may be used such as, for example, homopolymers, random co-polymers, block-copolymers, diblock-copolymers, trib
- the latex preferably comprises an aqueous cationic vinyl polymer.
- the latex comprises a polymer comprising styrene monomers, (meth)acry
- the porogens have an average particle size of 300 nm or less, preferably 200nm or less, more preferably 150 nm or less. In an aspect the porogens have an average particles size of 100 nm or less. In an aspect the porogens have an average particles size of 1 nm or more. Preferably the porogens have an average particle size of 10 nm or more. In aspect the porogens have an average particle size of 30 nm or more. Th average porogen size may be measured by Dynamic Light Scattering (DLS). Alternatively porogen size may be measured using Transmission Electron Microscopy (TEM).
- DLS Dynamic Light Scattering
- TEM Transmission Electron Microscopy
- the core- shell nanoparticles herein typically have an average particle size is 300 nm or less, preferably 200nm or less, more preferably 150 nm or less. In an aspect the nanoparticles have an average particles size of 100 nm or less. The core- shell nanoparticles particles have an average size of 1 nm or more.
- the core- shell nanoparticles have an average size of 10 nm or more.
- the core- shell nanoparticles have an average particle size of 30 nm or more.
- the average particle size may be measured by Dynamic Light Scattering (DLS).
- particle size may be measured using Transmission Electron Microscopy (TEM).
- g 300 nm or less.
- g 200 nm or less.
- g 150 nm or less.
- g 100 nm or less.
- g is 1 nm or more.
- g is 10 nm or more.
- the average size of the core of the core-shell nanoparticles is 1 nm or more, more preferably 3 nm or more, even more preferably 6 nm or more.
- the average size of the core is 100 nm or less, more preferably 80 nm or less,
- the size of the core may be measured using TEM.
- the core has an average size as measured using TEM of 6 nm or more and 100 nm or less. In an aspect the core has an average size as measured using TEM of 6 nm or more and 80 nm or less. In an aspect the core has an average size as measured using TEM of 10 nm or more and 70 nm or less.
- the shell of the core-shell nanoparticles has a thickness of at least 1 nm, more preferably of at least 5 nm, even more preferably of at least 10 nm.
- the shell has a thickness of 75 nm or less, more preferably 50 nm or less, even more preferably 25 nm or less. The shell thickness may be measured using TEM.
- the shell has a thickness as measured using TEM of 1 nm or more and 50 nm or less. In an aspect the shell has a thickness as measured using TEM of 5 nm or more and 25 nm or less. In an aspect the shell has a thickness as measured using TEM of 10 nm or more and 25 nm or less.
- the porogen accounts for 10 to 75 wt-% of the total amount of inorganic oxide equivalents in the coating formulation. In an aspect the porogen accounts for 20 to 50 wt-% of the total amount of inorganic oxide equivalents in the coating formulation.
- the inorganic binder typically comprises inorganic oxide particles with a diameter in the range of 0.1 to 7 nm and/or an inorganic oxide precursor with a diameter in the range of 0.1 to 7 nm.
- the inorganic binder is preferably an inorganic oxide particle or inorganic oxide precursor with a diameter in the order of 0.1 to 7 nm.
- the inorganic oxide particles may have a diameter of more than 7 nm, e.g. in the range of 7 to 10 nm. It is noted that the inorganic oxide precursor may have a diameter of more than 7 nm, e.g. in the range of 7 to 10 nm.
- the inorganic binder comprises inorganic oxide nanoparticles with an average diameter in the range of 0.1 to 7 nm.
- the inorganic binder typically comprises inorganic oxide particles with a diameter in the range of 0.1 to 5 nm and/or an inorganic oxide precursor with a diameter in the range of 0.1 to 5 nm.
- the diameter of the inorganic oxide particle and / or the inorganic oxide precursor may be measured with Dynamic Light Scattering (DLS).
- DLS Dynamic Light Scattering
- pre oligomerized silicium alkoxide such as pre oligomerized tetraethoxysilane, pre
- oligomerized titanium alkoxide and metal oxide sol gels An example of an inorganic oxide particle and / or the inorganic oxide precursor includes metal oxide sols.
- Pre oligomerized silicium alkoxide is also referred to by the skilled person as pre oligomerized silicon alkoxide.
- An inorganic binder may for example be prepared as described in WO
- the coating formulation according to the invention comprises a solvent.
- the solvent can be any solvent, combination of solvents or combination of solvents and additives, such as surfactants and stabilizers, that can realize a stable dispersion of the coating formulation.
- the solvent accounts for 80 - 98% of the mass of the coating formulation.
- Highly suitable solvents are isopropanol (IPA), water or combinations of solvents including IPA and/or water.
- the coating formulations according to the invention comprises elongated dense inorganic oxide particles with an aspect ratio of at least 2, and a smaller diameter in the range of 3 to 20 nm in a coating on a substrate for improving anti-soiling properties of a substrate. It was highly unexpected that the shape of the dense inorganic oxide particles appeared to have a major influence on the anti-soiling properties of the coating and that it hence was possible to reduce the sensitivity to soiling of a substrate by coating it with a coating where elongated dense inorganic oxide particles were included.
- a coating prepared from a coating formulation comprising non-spherical particles such as elongated particles, in particular elongated dense inorganic oxide particles demonstrates improved anti-soiling properties as compared to a coating prepared from a coating formulation without elongated dense inorganic oxide particles.
- a coating prepared from a coating formulation comprising non-spherical particles such as elongated particles, in particular elongated dense inorganic oxide particles demonstrates improved anti-soiling properties as compared to a coating prepared from a coating formulation comprising spherical particles.
- this method of reducing sensitivity to soiling of a substrate includes the steps of applying a coating formulation containing elongated dense inorganic oxide particles to a substrate, and convert the coating formulation into a functional coating for example by heating.
- Another aspect of the invention concerns a solar module comprising a coated substrate according to the invention.
- Another aspect of the invention concerns a solar module comprising a coated substrate as described herein.
- Such solar module exhibits significantly better performance over time at lower operational costs. The reason for that being the reduced frequency of cleaning or the improved power output at the same frequency of cleaning, all of which become possible due to the enhanced anti-soiling properties of the coating of the invention that significantly reduces the soiling of said solar module.
- Other advantageous devices comprising the coated substrate according to the invention are greenhouse glass (or polymer membrane), concentrated solar modules, windows, displays.
- the substrate may be non-transparent and the advantage of the invention is there focused on the ability of the anti-soiling coating to reduce collection of dirt on the substrate or to enhance cleanability of the coated substrate as compared to the uncoated substrate.
- the coating formulation may be applied to a substrate by any known technique in the art, for example dipping, brushing, spraying, spinning, slot die coating, aerosol coating or via the use of a roller. Spraying can be airless or with the use of conventional air, or electrostatic, or high volume/low pressure (HVLP) or aerosol coating. It is preferred that the coating formulation is applied by roll coating, aerosol coating or dip coating.
- functional coating is meant a coating that enhances mechanical, optical and/or electrical properties of the substrate to which the functional coating is attached.
- Examples of possible enhanced mechanical properties of a substrate coated with the coating of the invention are increased surface hardness, increased stiffness or wear properties as compared to the mechanical properties of the uncoated substrate.
- Examples of possible enhanced optical properties of a substrate coated with the coating of the invention are increased light transmittance from air through the functional coating and substrate compared to light transmittance directly from air through the substrate, and reduced reflectance from the interphase from air to the functional coating and the functional coating to the substrate compared to the reflectance directly from air to uncoated substrate.
- Examples of possible enhanced electrical properties of a substrate coated with the coating of the invention are increased conductivity as compared to the unconverted coating and/or to the uncoated substrate.
- Another aspect of the invention concerns the use of a coating formulation comprising elongated inorganic oxide particles with an aspect ratio of at least 2 and a smaller diameter in the range of 3 to 20 nm for improving anti-soiling properties of a substrate.
- this embodiment concerns a coating formulation comprising coreshell nanoparticle as porogen where the core comprises an organic compound, such as a cationic polymer or an organic compound with a boiling point below 200°C, and the shell comprises an inorganic oxide, and from 0.5 to 15 wt-% aluminium oxide equivalents of aluminium containing compound based on total ash rest after combustion at 600°C, 2 min in air.
- Another aspect of the invention includes the use of a coating formulation as described herein for improving anti-soiling properties of a substrate, such as a cover glass for a solar module.
- Another aspect of the invention includes the use of a coating formulation comprising elongated dense inorganic oxide particles with an aspect ratio of at least 2 and a smaller diameter in the range of 3 to 20 nm for improving anti-soiling properties of a substrate, wherein the coating formulation comprises core-shell nanoparticles as porogen, wherein the core comprises an organic compound, such as a polymer or an organic compound with a boiling point below 200°C, the shell comprises a inorganic oxide; and the formulation comprises from 0.5 to 15 wt-% aluminium oxide equivalents of aluminium containing compound.
- Another aspect of the invention includes the use of the combination of
- elongated dense inorganic oxide particles having an aspect ratio of at least 2 and a smaller diameter in the range of 3 to 20 nm;
- Another aspect of the invention includes the use of elongated dense inorganic oxide particles with an aspect ratio of at least 2, and a smaller diameter in the range of 3 to 20 nm to reduce the soiling of a solar module.
- Another aspect of the invention includes the use of the combination of
- a coating formulation comprising
- the coating formulation comprises of from 0.5 to 15 wt-% aluminium oxide equivalents of aluminium containing compound based on total ash rest after combustion at 600°C, 2 min in air.
- elongated dense oxide particles comprise elongated silica particles having an average diameter of from 3 to 20 nm and an average length of from 10 to 150 nm, preferably as measured from at least one TEM image.
- the elongated dense oxide particles are elongated silica particles having an average diameter of from 3 to 20 nm and an average length of from 10 to 150 nm, preferably as measured from at least one TEM image.
- the elongated dense oxide particles comprise elongated silica particles having an average diameter of from 2 to 20 nm and an average length of from 10 to 60 nm, preferably as measured from at least one TEM image.
- elongated dense oxide particles comprise elongated silica particles having an average diameter of from 2 to 20 nm and an average length of from 10 to 40 nm, preferably as measured from at least one TEM image.
- elongated dense oxide particles are elongated silica particles having an average diameter of from 2 to 20 nm and an average length of from 10 to 40 nm, preferably as measured from at least one TEM image.
- the elongated dense oxide particles comprise elongated silica particles having an average diameter of from 4 to 15 nm and an average length of from 40 to 100 nm, preferably as measured from at least one TEM image.
- the coating formulation comprises from 1 to 8 wt-% aluminium oxide equivalents of aluminium containing compound. 16. The coating formulation according to any one of the preceding embodiments, wherein the coating formulation comprises from 1 ,5 to 12 wt-% aluminium oxide equivalents of aluminium containing compound.
- coating formulation according to any one of the preceding embodiments, wherein the coating formulation comprises from 1 ,5 to 10 wt-% aluminium oxide equivalents of aluminium containing compound.
- coating formulation according to any one of the preceding embodiments, wherein the coating formulation comprises from 2 to 14 wt-% based on oxide equivalents of inorganics of elongated inorganic dense oxide particles.
- coating formulation according to any one of the preceding embodiments, wherein the coating formulation comprises from 2 to 13 wt-% based on oxide equivalents of inorganics of elongated inorganic dense oxide particles.
- coating formulation according to any one of the preceding embodiments, wherein the coating formulation comprises from 3 to 12 wt-% based on oxide equivalents of inorganics of elongated inorganic dense oxide particles.
- coating formulation according to any one of the preceding embodiments, wherein the coating formulation comprises from 4 to 12 wt-% based on oxide equivalents of inorganics of elongated inorganic dense oxide particles.
- coating formulation according to any one of the preceding embodiments, wherein the coating formulation comprises from 5 to 15 wt-% based on oxide equivalents of inorganics of elongated inorganic dense oxide particles.
- coating formulation according to any one of the preceding embodiments, wherein the coating formulation comprises from 5 to 12 wt-% based on oxide equivalents of inorganics of elongated inorganic dense oxide particles.
- the coating formulation comprises from 6 to 14 wt-% based on oxide equivalents of inorganics of elongated inorganic dense oxide particles.
- the coating formulation comprises from 6 to 13 wt-% based on oxide equivalents of inorganics of elongated inorganic dense oxide particles.
- the porogen comprises a core-shell nanoparticle wherein the core comprises an organic compound, and the shell comprises an inorganic oxide.
- porogen comprises triblock copolymer comprising poly(ethylene oxide) (PEO) and polypropylene oxide) (PPO).
- PEO poly(ethylene oxide)
- PPO polypropylene oxide
- the porogen comprises core-shell nanoparticle where the core comprises an organic compound, such as a cationic polymer or an organic compound with a boiling point below 200°C, and the shell comprises an inorganic oxide; and hollow inorganic nanoparticles.
- the inorganic binder comprises inorganic oxide nanoparticles with a number average diameter in the range of 0.1 to 7 nm.
- a method of preparing a coated substrate comprising the steps of
- a method of preparing a coated substrate comprising the steps of
- a coated substrate obtainable by a method according to any one of the preceding embodiments.
- a coated substrate obtainable by a method according to any one of the preceding embodiments, demonstrating improved anti-soiling properties.
- a coated substrate comprising:
- the anti-reflective coating comprises
- aluminium oxide equivalents of aluminium containing compound from 0.5 to 15 wt-% aluminium oxide equivalents of aluminium containing compound.
- the substrate comprises a transparent solid sheet member, and a base coating layer interposed between the first surface and the coating layer on the first surface, preferably the base coating is selected from the group of barrier coatings and anti- reflective coatings.
- the coated substrate according to any one of the preceding embodiments, wherein the substrate is a polymer sheet or a glass member, preferably the glass member comprises structured glass such as MM or SM glass.
- the substrate comprises a transparent solid sheet member with a base coating on a first side of the sheet member so the base coating forms at least a part of the first surface of the substrate, preferably the base coating is selected from the group of barrier coatings and anti-reflective coatings.
- the mass ratio of inorganic oxide originating from the dense inorganic oxide particles to total inorganic oxide of the coating is at least 50% higher in the 20 nm of the coating closest to the outer surface than the average mass ratio of the inorganic oxide originating from dense inorganic oxide particles to total inorganic oxide of the coating,
- the mass ratio of inorganic oxide originating from the dense inorganic oxide particles to total inorganic oxide of the coating is at least twice as high in the 20 nm of the coating closest to the outer surface than the average mass ratio of the inorganic oxide originating from dense inorganic oxide particles to total inorganic oxide of the coating.
- the coated substrate according to any one of the preceding embodiments, wherein the substrate demonstrates a substrate-coating anti-soiling ratio, ASR, with is at least 55%, wherein T is the average transmittance in the wavelength range from 380-1 100 nm, Substrate refers to substrate without coating, Coating refers to the substrate with double sided coating, 0 refers to before soil test and soil refers to after soil test.
- ASR substrate-coating anti-soiling ratio
- coated substrate according to any one of the preceding embodiments, wherein the substrate demonstrates a substrate-coating anti-soiling ratio, ASR, of 60%.
- ASR is at least 65%.
- ASR is at least
- ASR is at least 90%.
- T is the average transmittance in the wavelength range from 380-1 100 nm
- Substrate refers to substrate without coating
- Coated substrate refers to the substrate with double sided coating
- 0 refers to before soil test.
- the mass ratio of inorganic oxide originating from the dense inorganic oxide particles to total inorganic oxide of the coating is at least 50% higher in the top layer of the coating than the average mass ratio of the inorganic oxide originating from elongated dense inorganic oxide particles to total inorganic oxide of the coating,
- the mass ratio of inorganic oxide originating from the elongated dense inorganic oxide particles to total inorganic oxide of the coating is at least twice as high in the top layer the coating than the average mass ratio of the inorganic oxide originating from dense inorganic oxide particles to total inorganic oxide of the coating.
- a solar module comprising a coated substrate according to any one of the preceding embodiments.
- composition according to any one of the preceding embodiments to reduce the frequency of cleaning of substrate, preferably glass.
- composition according to any one of the preceding embodiments to improve anti-soiling properties of a substrate, preferably glass
- composition according to any one of the preceding embodiments to reduce the frequency of cleaning of a cover glass of a solar module.
- composition according to any one of the preceding embodiments to improve anti-soiling properties of the cover glass of a solar module.
- optical properties were measured in the wavelength region from 380-1 100 nm using an Optosol Transpec VIS-NIR spectrophotometer equipped with an integrating sphere. The average transmittance and Max T% (l at Max) are determined. The results are listed below.
- Soiling procedure The anti-soiling properties of the coatings was tested with a Taber Oscillating Abrasion Tester (model 6160) using commercially available Arizona test dust from quartz A4 coarse (size varying from 1 to 200 pm) as soiling medium, commercially available from KSL Staubtechnik GMBH.
- the 100 x 100 mm glass plate to be tested were first cleaned with deionized water and a soft cloth, rinsed with laboratory grade ethanol and left to dry overnight.
- the coated sample was then placed in the tray of the Taber Oscillating table so that the top surface of the glass plate was at the same height as the sample holder inside the tray.
- 20 g of Arizona test dust was gently dispersed over the whole glass plate using a brush.
- the soiling procedure (300 cycles at a speed of 100 cycles per minute; one cycle is defined as a full revolution of the circular drive disk: one completed back-and-forth movement of the tray) was performed.
- the test sample was then removed from the tray and gently tapped to remove the excess of sand on its surface.
- the back side of the tested glass plate was gently wiped with a soft cloth to remove any dust adhering under the plate.
- the relative humidity in the testing environment was at 36 %RH and the temperature was 21 °C.
- Soiling evaluation The degree of soiling of the coatings was determined by relative loss in transmittance after soiling, measured with Optosol Transpec VIS-NIR spectrophotometer. To that end, transmittance spectra were recorded prior and post artificial soiling via the Taber Oscillating Abrasion Tester. Subsequently, the average of transmittance over 380-1 100 nm spectra is established. Based on the resulting differences between the before and after values of the average transmittance over 380-1 100 nm recorded in the spectra, conclusions regarding the level of soiling and hence the effectiveness of the anti-soiling coatings can be drawn.
- Pore size of porogen pores i.e. pores with a diameter in the range of 10 to 120 nm, is defined as the length of a line indicating the longest distance between walls of the pore on a cross section orthogonal to the surface of the substrate as measured by SEM. For irregular pore, the line indicating the longest distance may go outside pore. As is well known SEM stands for Scanning Electron Microscopy.
- ellipsometry is used to measure the pore size, using the method indicated herein. Since the method utilizes sorption of water in the pores, the measured size corresponds to the smallest diameter of the pore.
- the size of the binder particles and the size of the elongated dense inorganic particles are measured using CryoTEM.
- the average size is the number average size based on ten randomly selected particles.
- the volume fraction and pore size distribution of binder pores are determined by water sorption under variation of relative partial pressure of water.
- the saturation pressure (and hence condensation/evaporation of water in the pores) is a function of the smallest dimension of the pore as described by the Kelvin equation. Condensation of water in the pores drastically changes the optical properties of the coating due to the difference in density between water and air, which optical properties are measured by ellipsometry.
- Sample preparation depends on substrate type.
- a scotch tape was applied on the backside of the glass to reduce backside reflections.
- measurement is done using focusing probes to reduce light scattering induced by the sample roughness.
- No scotch tape is applied at the backside in the case of SM glass.
- the ellipsometer used is a Woollam M-2000 Ul running CompleteEase (Woollam) version 5.20.
- the refractive index herein is reported at an optical wavelength of 600 nm.
- the experimental data are analyzed by fitting to optical models built using CompleteEase.
- the bare, uncoated substrate is measured first and then fitted using a b- spline model.
- the coating layer is described by a Cauchy model, using the first two terms of the series development, A and B.
- the data measured at 35% rH was used.
- Core-shell particles were prepared by the same method as disclosed in W02009/030703 using isopropanol instead of ethanol. The solution was further diluted with isopropanol to a concentration of 10.0 wt-% silica equivalents and had a particle size of 135 nm.
- Silica based inorganic binder was prepared from tetraethoxysilane was prepared by the same method as disclosed in WO 201 1/157820 and further diluted with isopropanol to achieve a binder solution of about 2 wt-% silica equivalents and a particle size of 3-5 nm.
- Al-Stock solution was prepared by dissolving AI(N0 3 ) 3 .9H20 (Fluka, 06275 Lot SZBG0830V) into a mixture of isopropanol (Brenntag, batch 1/103/3jul 15/13333, Ref 2427801 ) and methoxypropanol (Sigma Aldrich, Lot K49958738820) to a solid content of 5%. Thereafter the solution was further diluted with isopropanol to 2 wt-% alumina equivalents.
- IPA-ST-UP elongated IPA-ST-UP particles
- IPA-ST-UP Nasan Chemical, Lot 1 1 1002
- isopropanol a concentration of 2 wt-% of oxide equivalents. This stock solution was used to prepare the samples in Table 1.
- Coatings were prepared with coating formulations that were used were maximum 48 h old. All samples were soiled within 48 h after preparation of the coating. Formulations were filled into a rectangular shaped container, with an inner size of 2.5 * 11 * 1 1 cm filled with approximately 200 g of coating formulation.
- Example 6 Conversion of applied coating formulation into a functional coating
- the coated samples listed in table 1 were dried at least 15 minutes at room temperature and thereafter cured by heating in an oven at 650°C for 3.5 minutes. This treatment is like the thermal conversion realized during the tempering process typically used for cover glass for PV solar modules.
- the results of the optical measurements are listed in Table 2.
- Fig. 2 the transmission measurement for sample E according to the invention is shown. Here, the transmission before and after soiling are very close.
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Application Number | Priority Date | Filing Date | Title |
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EP18200804 | 2018-10-16 | ||
EP19161387 | 2019-03-07 | ||
PCT/EP2019/077918 WO2020078977A1 (en) | 2018-10-16 | 2019-10-15 | Coating and coating formulation |
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CN (1) | CN112840000B (en) |
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Publication number | Priority date | Publication date | Assignee | Title |
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EP1818694A1 (en) | 2006-02-14 | 2007-08-15 | DSMIP Assets B.V. | Picture frame with an anti reflective glass plate |
US20100249297A1 (en) | 2007-09-05 | 2010-09-30 | Thies Jens Christoph | Novel nanoparticles |
CN101959822A (en) | 2008-02-29 | 2011-01-26 | 帝斯曼知识产权资产管理有限公司 | Articles comprising coating |
WO2010043653A1 (en) * | 2008-10-14 | 2010-04-22 | Dsm Ip Assets B.V. | Stain resistant particles |
MY160973A (en) * | 2010-06-18 | 2017-03-31 | Dsm Ip Assets Bv | Inorganic oxide coating |
AU2011298373A1 (en) * | 2010-09-01 | 2013-04-11 | Agc Flat Glass North America, Inc. | Glass substrate coated with an anti-reflective layer |
US9561525B2 (en) * | 2011-02-11 | 2017-02-07 | Dsm Ip Assets B.V. | Process for depositing an anti-reflective layer on a substrate |
KR101653894B1 (en) * | 2012-01-23 | 2016-09-02 | 아사히 가세이 이-매터리얼즈 가부시키가이샤 | Coating composition and antireflection film |
EP2752386B1 (en) * | 2012-12-13 | 2019-08-28 | Guardian Glass, LLC | Method of making coated article including anti-reflection coating with porosity differences in two layers, and products containing the same |
US9359249B2 (en) * | 2013-05-29 | 2016-06-07 | Guardian Industries Corp. | Anti-corrosion anti-reflection glass and related methods |
CN110520484B (en) * | 2017-04-18 | 2023-01-31 | 科思创(荷兰)有限公司 | Coatings and coating formulations |
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CN112840000A (en) | 2021-05-25 |
WO2020078977A1 (en) | 2020-04-23 |
TW202024247A (en) | 2020-07-01 |
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