WO2022209835A1 - 積層体 - Google Patents
積層体 Download PDFInfo
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- WO2022209835A1 WO2022209835A1 PCT/JP2022/011432 JP2022011432W WO2022209835A1 WO 2022209835 A1 WO2022209835 A1 WO 2022209835A1 JP 2022011432 W JP2022011432 W JP 2022011432W WO 2022209835 A1 WO2022209835 A1 WO 2022209835A1
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- Prior art keywords
- fine particles
- glass
- functional film
- glass plate
- content
- Prior art date
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- 239000011521 glass Substances 0.000 claims abstract description 141
- 239000011941 photocatalyst Substances 0.000 claims abstract description 40
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 25
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 25
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 239000010419 fine particle Substances 0.000 claims description 121
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 59
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- 230000000844 anti-bacterial effect Effects 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 25
- 229910021645 metal ion Inorganic materials 0.000 claims description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 7
- 229910001431 copper ion Inorganic materials 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 3
- 239000011859 microparticle Substances 0.000 abstract 3
- 238000003426 chemical strengthening reaction Methods 0.000 description 19
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- 229910052814 silicon oxide Inorganic materials 0.000 description 14
- 238000000576 coating method Methods 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 12
- -1 silicon oxide Chemical class 0.000 description 12
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- 239000011734 sodium Substances 0.000 description 11
- 238000006124 Pilkington process Methods 0.000 description 10
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- 239000000203 mixture Substances 0.000 description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 125000004430 oxygen atom Chemical group O* 0.000 description 7
- 229910052718 tin Inorganic materials 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000006060 molten glass Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 229910018068 Li 2 O Inorganic materials 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000156 glass melt Substances 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 235000010333 potassium nitrate Nutrition 0.000 description 5
- 239000004323 potassium nitrate Substances 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 239000005341 toughened glass Substances 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000005329 float glass Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 101100258086 Postia placenta (strain ATCC 44394 / Madison 698-R) STS-01 gene Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
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- 238000011049 filling Methods 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
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- 230000000717 retained effect Effects 0.000 description 1
- 238000007372 rollout process Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/068—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/025—Particulate layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/408—Matt, dull surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
- B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
-
- 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
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/45—Inorganic continuous phases
-
- 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
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
- C03C2217/477—Titanium oxide
-
- 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
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
- C03C2217/478—Silica
-
- 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
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/48—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific function
Definitions
- the present invention relates to laminates.
- Patent Document 1 discloses a glass article on which a functional film containing silica fine particles and titanium oxide fine particles is formed. This glass article is supposed to have both a photocatalytic function and an antireflection function.
- the present invention has been made to solve this problem, and an object of the present invention is to provide a laminate having both a photocatalytic function and a reflection suppressing function.
- Section 1 a substrate having a first side and a second side; a functional film formed on the first surface; with The functional membrane is a binder containing a metal oxide that forms a three-dimensional network bond; Metal oxide fine particles held by the binder and dispersed in a single layer; photocatalyst fine particles arranged between the metal oxide fine particles; A laminate containing
- Section 2. The laminate according to Item 1, wherein the ratio of the mass of the metal oxide fine particles to the total mass of the inorganic oxide fine particles and the binder contained in the functional film is greater than 0.4.
- the metal oxide fine particles are formed of silica, Item 3.
- Section 4. The laminate according to any one of Items 1 to 3, wherein the content of the photocatalyst fine particles in the functional film is 35% by mass or more.
- Item 5. The laminate according to any one of Items 1 to 4, wherein the content of the metal oxide fine particles in the functional film is 50% by mass or less.
- Item 6. The laminate according to any one of Items 1 to 5, wherein the distance between adjacent metal oxide fine particles is less than 1 ⁇ m.
- Item 7. The laminate according to any one of Items 1 to 6, wherein the photocatalyst fine particles are laminated between the metal oxide fine particles.
- Item 8 The laminate according to any one of Items 1 to 7, wherein the average particle size of the metal oxide fine particles is at least five times the average particle size of the photocatalyst fine particles.
- Item 9 The laminate according to any one of Items 1 to 8, wherein the photocatalyst fine particles have a higher refractive index than the substrate.
- Item 10 The laminate according to any one of Items 1 to 9, wherein the functional film contains an antibacterial metal ion.
- Item 11 The laminate according to Item 10, wherein the metal ions are copper ions.
- Item 12. The laminate according to any one of Items 1 to 11, wherein the substrate is a glass plate.
- FIG. 2 is a cross-sectional view showing an example of a schematic diagram of the functional film of FIG. 1; 5 is a graph showing the relationship between wavelength and transmittance in Examples 1 to 5.
- FIG. 10 is a graph showing the relationship between wavelength and transmittance of Examples 6 to 12.
- FIG. 10 is a graph showing the relationship between wavelength and reflectance in Examples 13-15.
- 1 is a SEM photograph of the surface and cross section of the antibacterial film of Example 1.
- the glass member according to the present embodiment can be used in various applications such as, for example, as a glass member for covering an article or as a part of a structure.
- goods include mobile PCs, tablet PCs, in-vehicle devices such as car navigation systems, devices that at least partially have a display function using electronic components, and external displays that do not have an electronic display function.
- Various devices such as a display device for displaying some kind of display are targeted.
- a product to be shown to the outside such as a product
- Examples of the above structures include various structures using glass, such as buildings, cases such as showcases, glass plates of copiers, partitions, and the like.
- Fig. 1 is a cross-sectional view of the glass member.
- a glass member 10 according to this embodiment includes a glass plate 1 having a first surface and a second surface, and a functional film 2 laminated on the first surface of the glass plate 1. ing.
- this glass member 10 is used as a cover member, it is arranged so as to cover the article 100 described above.
- the second surface of the glass plate 1 is arranged to face the article 100, and the functional film 2 is arranged to face the outside.
- the functional film 2 is arranged to face the outside.
- the glass plate 1 can be made of general-purpose soda-lime glass, borosilicate glass, aluminosilicate glass, alkali-free glass, or other glass, for example. Further, the glass plate 1 can be formed by a float method. According to this manufacturing method, a glass plate 1 having a smooth surface can be obtained. However, the glass plate 10 may have unevenness on its main surface, and may be a figured glass, for example. A figured glass can be molded by a manufacturing method called a roll-out method. A figured glass produced by this method usually has periodic irregularities in one direction along the main surface of the glass plate.
- molten glass is continuously supplied onto molten tin or other molten metal, and the supplied molten glass is made to flow on the molten metal to form a strip.
- the glass thus formed is called a glass ribbon.
- the glass ribbon is cooled as it goes downstream, is cooled and solidified, and is pulled up from the molten metal by rollers. Then, it is conveyed to a slow cooling furnace by rollers, and cut after slow cooling. A float glass sheet is thus obtained.
- the thickness of the glass plate 1 is not particularly limited, it should be thinner for weight reduction.
- it is preferably 0.3 to 5 mm, more preferably 0.6 to 2.5 mm. This is because if the glass plate 10 is too thin, the strength will decrease, and if it is too thick, the article 100 viewed through the glass member 10 may be distorted.
- the glass plate 1 may generally be a flat plate, but may also be a curved plate.
- the glass plate 1 preferably has a non-planar main surface that conforms thereto.
- the glass plate 1 may be bent so as to have a constant curvature as a whole, or may be bent locally.
- the main surface of the glass plate 1 may be configured by, for example, connecting a plurality of flat surfaces with curved surfaces.
- the radius of curvature of the glass plate 1 can be, for example, 5000 mm or less.
- the lower limit of the radius of curvature can be, for example, 10 mm or more, but it may be even smaller, for example, 1 mm or more, especially in a locally bent portion.
- a glass plate having the following composition can also be used.
- percentages indicating the components of the glass plate 1 all mean mol%.
- the phrase “substantially composed of” means that the total content of the listed components is 99.5% by mass or more, preferably 99.9% by mass or more, more preferably 99.95% by mass. It means that it occupies more than % by mass. “Substantially free” means that the content of the component is 0.1% by mass or less, preferably 0.05% by mass or less.
- SL in a narrow sense a glass composition suitable for the production of glass plates by the float method
- the composition range considered by those skilled in the art to be soda lime silicate glass suitable for the float process hereinafter sometimes referred to as “broadly defined SL”
- mass% range in which the properties such as T 2 and T 4 are approximated to SL in the narrow sense as much as possible while improving the chemical strengthening properties of SL in the narrow sense.
- SiO2 is a main component that constitutes the glass plate 1. If the content is too low, the chemical durability such as water resistance and heat resistance of the glass are lowered. On the other hand, if the SiO 2 content is too high, the viscosity of the glass plate 1 at high temperatures becomes high, making melting and molding difficult. Therefore, the content of SiO 2 is suitably in the range of 66-72 mol %, preferably 67-70 mol %.
- Al2O3 Al 2 O 3 improves the chemical durability such as water resistance of the glass plate 1, and facilitates the movement of alkali metal ions in the glass to increase the surface compressive stress after chemical strengthening. It is a component for deepening the depth.
- the content of Al 2 O 3 is too high, the viscosity of the glass melt will increase, T 2 and T 4 will increase, and the clarity of the glass melt will deteriorate, making it difficult to produce a high-quality glass plate. becomes difficult.
- the content of Al 2 O 3 is appropriately in the range of 1 to 12 mol %.
- the content of Al 2 O 3 is preferably 10 mol % or less, preferably 2 mol % or more.
- the glass plate 1 preferably contains MgO.
- MgO MgO
- the content of MgO is less than 8 mol %, the surface compressive stress after chemical strengthening tends to decrease and the depth of the stress layer tends to become shallow.
- the strengthening performance obtained by chemical strengthening is lowered, and in particular the depth of the surface compressive stress layer is sharply reduced.
- MgO has the least adverse effect, but in this glass plate 1, the content of MgO is 15 mol % or less.
- T 2 and T 4 are increased and the clarity of the glass melt is deteriorated, making it difficult to produce a high-quality glass plate.
- the content of MgO is in the range of 1 to 15 mol%, preferably 8 mol% or more and 12 mol% or less.
- CaO CaO has the effect of lowering the viscosity at high temperatures, but if the content is too high beyond an appropriate range, the glass plate 1 tends to devitrify and the movement of sodium ions in the glass plate 1 is inhibited. end up When CaO is not contained, the surface compressive stress after chemical strengthening tends to decrease. On the other hand, if the CaO content exceeds 8 mol %, the surface compressive stress after chemical strengthening is significantly reduced, the depth of the compressive stress layer is significantly reduced, and the glass plate 1 is likely to devitrify.
- the appropriate CaO content is in the range of 1 to 8 mol%.
- the CaO content is preferably 7 mol % or less, and preferably 3 mol % or more.
- SrO, BaO greatly lower the viscosity of the glass plate 1, and when contained in small amounts, the effect of lowering the liquidus temperature TL is more pronounced than CaO.
- SrO and BaO significantly hinder the movement of sodium ions in the glass plate 1, greatly reduce the surface compressive stress, and make the depth of the compressive stress layer considerably shallow.
- the glass plate 1 does not substantially contain SrO and BaO.
- ( Na2O ) Na 2 O is a component for increasing the surface compressive stress and increasing the depth of the surface compressive stress layer by replacing sodium ions with potassium ions.
- the stress relaxation during the chemical strengthening treatment will exceed the generation of surface compressive stress due to ion exchange during the chemical strengthening treatment, and as a result, the surface compressive stress will tend to decrease. be.
- Na 2 O is a component for improving the solubility and lowering T 4 and T 2 , but if the content of Na 2 O is too high, the water resistance of the glass is remarkably lowered.
- the content of Na 2 O is 10 mol % or more, the effect of reducing T 4 and T 2 is sufficiently obtained, and if it exceeds 16 mol %, the surface compressive stress is significantly reduced due to stress relaxation. Become.
- the content of Na 2 O in the glass plate 1 of this embodiment is appropriately in the range of 10 to 16 mol %.
- the Na 2 O content is preferably 12 mol % or more, and more preferably 15 mol % or less.
- K2O K 2 O like Na 2 O, is a component that improves the solubility of glass.
- the ion exchange rate in chemical strengthening increases, the depth of the surface compressive stress layer increases, and the liquidus temperature TL of the glass plate 1 decreases. Therefore, it is preferable to contain K 2 O at a low content.
- K 2 O is less effective than Na 2 O in reducing T 4 and T 2 , but a large amount of K 2 O inhibits clarification of the glass melt. Also, the higher the K 2 O content, the lower the surface compressive stress after chemical strengthening. Therefore, the appropriate K 2 O content is in the range of 0 to 1 mol %.
- the glass plate 1 of the present embodiment may contain Li 2 O in an amount of 1 mol % or less, but preferably does not substantially contain Li 2 O.
- B2O3 is a component that lowers the viscosity of the glass plate 1 and improves its solubility.
- the content of B 2 O 3 is too high, the glass plate 1 tends to undergo phase separation and the water resistance of the glass plate 1 decreases.
- the compound formed by B 2 O 3 and the alkali metal oxide may volatilize and damage the refractories in the glass melting chamber.
- the inclusion of B 2 O 3 reduces the depth of the compressive stress layer in chemical strengthening. Therefore, the appropriate content of B 2 O 3 is 0.5 mol % or less. In the present invention, it is more preferable that the glass plate 1 does not substantially contain B 2 O 3 .
- Fe2O3 Fe usually exists in the glass in the form of Fe 2+ or Fe 3+ and acts as a colorant.
- Fe 3+ is a component that enhances the ultraviolet absorption performance of the glass
- Fe 2+ is a component that enhances the heat ray absorption performance.
- the iron oxide content in terms of Fe 2 O 3 is preferably 0.15% by mass or less, more preferably 0.1% by mass or less, when the entire glass plate 1 is taken as 100% by mass. It is preferably 0.02% by mass or less, more preferably 0.02% by mass or less.
- TiO2 TiO 2 is a component that lowers the viscosity of the glass plate 1 and increases the surface compressive stress due to chemical strengthening. Therefore, the appropriate content of TiO 2 is 0 to 0.2% by mass. In addition, it is inevitably mixed with commonly used industrial raw materials, and may be contained in the glass plate 1 in an amount of about 0.05% by mass. This level of content does not color the glass, so it may be included in the glass plate 1 of the present embodiment.
- ZrO2 ZrO 2 may be mixed into the glass plate 1 from the refractory bricks constituting the glass melting kiln, especially when the glass plate is manufactured by the float method, and its content is about 0.01% by mass.
- ZrO 2 is a component that improves the water resistance of glass and increases surface compressive stress due to chemical strengthening.
- a high ZrO 2 content may cause an increase in the working temperature T 4 and a rapid increase in the liquidus temperature TL . It tends to remain as a foreign substance in the manufactured glass. Therefore, the appropriate ZrO 2 content is 0 to 0.1% by mass.
- SO3 In the float method, sulfates such as Glauber's salt (Na 2 SO 4 ) are commonly used as clarifiers. Sulfate decomposes in the molten glass to produce gas components, which promotes defoaming of the glass melt, but some of the gas components dissolve and remain in the glass plate 1 as SO 3 .
- SO 3 is preferably 0 to 0.3% by mass.
- CeO2 CeO 2 is used as a fining agent. CeO 2 contributes to degassing since it produces O 2 gas in the molten glass. On the other hand, too much CeO 2 causes the glass to turn yellow. Therefore, the CeO 2 content is preferably 0 to 0.5% by mass, more preferably 0 to 0.3% by mass, and even more preferably 0 to 0.1% by mass.
- SnO2 It is known that in a glass sheet molded by the float method, tin diffuses from the tin bath to the surface that comes into contact with the tin bath during molding, and the tin exists as SnO 2 . Also, SnO 2 mixed with the glass raw material contributes to defoaming. In the glass plate 1 of the present invention, SnO 2 is preferably 0 to 0.3% by mass.
- the glass plate 1 according to the present embodiment is substantially composed of the components listed above.
- the glass plate 1 according to the present embodiment may contain components other than the components listed above, preferably within a range where the content of each component is less than 0.1% by mass.
- components that are allowed to be included include As2O5 , Sb2O5 , Cl , and F, which are added for the purpose of defoaming the molten glass , in addition to SO3 and SnO2 described above.
- As 2 O 5 , Sb 2 O 5 , Cl, and F are preferably not added because they have a large adverse effect on the environment.
- other examples that are allowed to be included are ZnO , P2O5 , GeO2 , Ga2O3 , Y2O3 and La2O3 .
- Components other than the above derived from industrially used raw materials are acceptable as long as they do not exceed 0.1% by mass. Since these components are added as appropriate or mixed inevitably as necessary, the glass plate 1 of the present embodiment may be substantially free of these components. do not have.
- the density of the glass plate 1 is reduced to 2.53 g ⁇ cm ⁇ 3 or less, further 2.51 g ⁇ cm ⁇ 3 or less, and in some cases 2.50 g ⁇ cm ⁇ 3 or less. be able to.
- the density of soda-lime glass currently mass-produced by the float method is about 2.50 g ⁇ cm ⁇ 3 . Therefore, considering mass production by the float method, the density of the glass plate 1 should be close to the above values, specifically 2.45 to 2.55 g ⁇ cm ⁇ 3 , particularly 2.47 to 2.53 g ⁇ cm ⁇ 3 . cm ⁇ 3 is preferred, and 2.47 to 2.50 g ⁇ cm ⁇ 3 is more preferred.
- the glass substrate may warp.
- the elastic modulus of the glass plate 1 is high.
- the elastic modulus (Young's modulus: E) of the glass plate 1 can be increased to 70 GPa or higher, or even 72 GPa or higher.
- Chemical strengthening of the glass plate 1 will be described below. (Chemical strengthening conditions and compressive stress layer)
- a glass plate 1 containing sodium is brought into contact with a molten salt containing monovalent cations having an ionic radius larger than that of sodium ions, preferably potassium ions, so that the sodium ions in the glass plate 1 are replaced with the above monovalent cations.
- the chemical strengthening of the glass plate 1 according to the present invention can be carried out by performing an ion-exchange treatment that replaces with . Thereby, a compressive stress layer having a compressive stress applied to the surface is formed.
- Potassium nitrate can typically be mentioned as the molten salt.
- a mixed molten salt of potassium nitrate and sodium nitrate can also be used, but since it is difficult to control the concentration of the mixed molten salt, a molten salt of potassium nitrate alone is preferable.
- the surface compressive stress and compressive stress layer depth in the tempered glass member can be controlled not only by the glass composition of the article, but also by the temperature and treatment time of the molten salt in the ion exchange treatment.
- a tempered glass member having a very high surface compressive stress and a very deep compressive stress layer can be obtained. Specifically, a tempered glass member having a surface compressive stress of 700 MPa or more and a compressive stress layer having a depth of 20 ⁇ m or more can be obtained. Certain tempered glass members can also be obtained.
- wind tempering can be used as a general strengthening method instead of chemical strengthening.
- FIG. 2 is an enlarged cross-sectional view schematically showing the vicinity of the surface of the functional film.
- the functional film 2 includes an inorganic oxide forming a three-dimensional network bond, inorganic oxide fine particles held by the inorganic oxide, and photocatalyst fine particles held by the inorganic oxide. Antibacterial metal ions can also be added, if desired. These will be described below.
- the inorganic oxide serves as a binder that holds the inorganic oxide fine particles and metal ions.
- the inorganic oxide includes, for example, silicon oxide, which is an oxide of Si, and preferably contains silicon oxide as a main component. Using silicon oxide as a main component is suitable for lowering the refractive index of the film and suppressing the reflectance of the film.
- the functional film may contain a component other than silicon oxide, or may contain a component partially containing silicon oxide.
- the component partially containing silicon oxide forms, for example, a three-dimensional network structure of siloxane bonds (Si--O--Si) in which silicon atoms and oxygen atoms are alternately connected and spread three-dimensionally. Also, it is a component in which atoms other than both atoms, functional groups, and the like are bonded to silicon atoms or oxygen atoms in this portion. Examples of atoms other than silicon atoms and oxygen atoms include nitrogen atoms, carbon atoms, hydrogen atoms, and metal elements described in the next paragraph. Examples of functional groups include organic groups described as R in the next paragraph. Such components are not strictly silicon oxides in that they are not composed only of silicon and oxygen atoms.
- the silicon oxide portion composed of silicon atoms and oxygen atoms is also consistent with the common practice in the field.
- the silicon oxide portion is also treated as silicon oxide.
- the atomic ratio of silicon atoms and oxygen atoms in silicon oxide need not be stoichiometric (1:2).
- the functional film 2 may contain metal oxides other than silicon oxide, specifically metal oxide components or metal oxide portions containing other than silicon.
- the metal oxide that the functional film 2 may contain is not particularly limited, but for example, an oxide of at least one metal element selected from the group consisting of Al, Ti, Zr, Ta, Nb, Nd, La, Ce and Sn. is.
- the functional film 2 may contain inorganic compound components other than oxides, such as nitrides, carbides, and halides, or may contain organic compound components.
- Metal oxides such as silicon oxide, can be formed from hydrolyzable organometallic compounds.
- hydrolyzable silicon compounds include compounds represented by formula (1).
- RnSiY4 -n ( 1)
- R is an organic group containing at least one selected from an alkyl group, a vinyl group, an epoxy group, a styryl group, a methacryloyl group and an acryloyl group.
- Y is at least one hydrolyzable organic group selected from an alkoxy group, an acetoxy group, an alkenyloxy group and an amino group, or a halogen atom.
- a halogen atom is preferably Cl.
- n is an integer from 0 to 3, preferably 0 or 1;
- R is preferably an alkyl group, such as an alkyl group having 1 to 3 carbon atoms, particularly a methyl group.
- Y is preferably an alkoxy group such as an alkoxy group having 1 to 4 carbon atoms, particularly a methoxy group and an ethoxy group.
- Two or more of the compounds represented by the above formulas may be used in combination. Such a combination includes, for example, a combination of a tetraalkoxysilane in which n is 0 and a monoalkyltrialkoxysilane in which n is 1.
- the compound represented by formula (1) forms a network structure in which silicon atoms are bonded to each other via oxygen atoms.
- the organic group represented by R is included directly attached to the silicon atom.
- the content of the inorganic oxide in the functional film 2 is preferably 5-50% by mass, more preferably 10-40% by mass. If the content of the inorganic oxide is large, the antireflection function is reduced as described later, which is not preferable. On the other hand, when the content of the inorganic oxide is small, the adhesion area between the fine particles and the glass plate 1 becomes small, resulting in poor abrasion resistance.
- the functional film 2 further contains inorganic oxide fine particles as at least part of the inorganic oxide.
- the inorganic oxide fine particles are generally dispersed in one layer on one glass plate.
- the inorganic oxide constituting the inorganic oxide fine particles is, for example, an oxide of at least one element selected from Si, Al, Ti, Zr, Ta, Nb, Nd, La, Ce and Sn.
- a plurality of kinds of inorganic oxide fine particles can also be contained.
- Silica fine particles for example, can be used as the inorganic oxide fine particles having a large average particle size.
- Silica fine particles can be introduced into the functional film 2 by adding colloidal silica, for example.
- the inorganic oxide fine particles are excellent in transferring the stress applied to the functional film 2 to the glass plate 1 supporting the functional film 2 and have high hardness. Therefore, addition of inorganic oxide fine particles is advantageous from the viewpoint of improving the abrasion resistance of the functional film 2 .
- the inorganic oxide fine particles can be supplied to the functional film 2 by adding preformed inorganic oxide fine particles to the coating liquid for forming the functional film 2 .
- the average particle diameter of the inorganic oxide fine particles is preferably, for example, 50 to 150 nm, more preferably 80 to 130 nm. Also, the average particle size of the inorganic oxide fine particles is preferably larger than the film thickness of the functional film 2 . Also, the average particle size of the inorganic oxide fine particles is preferably at least five times the average particle size of the photocatalyst fine particles described later. When the average particle size of the photocatalyst particles is small in this way, the effect of the apparent refractive index is reduced, so reflection can be suppressed.
- the average particle size of the inorganic oxide fine particles is described in the state of primary particles. This point is the same for photocatalyst fine particles to be described later.
- the average particle diameter of the inorganic oxide fine particles is determined by measuring the particle diameters of 50 arbitrarily selected fine particles by observation using a scanning electron microscope and adopting the average value. If the content of the inorganic oxide fine particles increases, the functional film 2 may become cloudy.
- the content of the inorganic oxide fine particles in the functional film 2 is preferably 10 to 50% by mass, preferably 15 to 45% by mass.
- the ratio of the content of the inorganic oxide fine particles to the total content of the inorganic oxide fine particles and the inorganic oxide (binder) is preferably greater than 0.4. That is, considering the relationship between the fine particles of inorganic oxide and the binder, it is preferable that the content of the binder is small as described above.
- the inorganic oxide fine particles are dispersed on the glass plate, and the interval between adjacent inorganic oxide fine particles is preferably within 1 ⁇ m. This is because if the distance is too large, the width of the unevenness formed on the surface of the functional film is widened, making it difficult to lower the apparent refractive index.
- the inorganic oxide fine particles are laminated in multiple layers between adjacent inorganic oxide fine particles.
- the photocatalyst fine particles for example, fine particles such as titanium oxide (TiO 2 ) and cerium oxide (CeO 2 ) can be used.
- the average particle size of the photocatalyst fine particles is smaller than the average particle size of the inorganic oxide fine particles such as the silica fine particles described above, and is preferably 1 to 50 nm, more preferably 25 to 30 nm.
- the content of the photocatalyst fine particles in the functional film 2 is preferably 35 to 70 mass %, preferably 40 to 60 mass %.
- the refractive index of the photocatalyst fine particles can be, for example, 2.0 to 2.8. This refractive index may be greater than that of the glass plate 1, which is the substrate.
- the content of metal ions in the functional film 2 is, for example, preferably 1 to 30% by mass of the functional film 2, more preferably 3 to 15% by mass.
- the thickness of the functional film 2 is, for example, preferably 10-200 nm, more preferably 50-150 nm. If the thickness is too thick, the haze ratio may increase or excessive coloring may occur. On the other hand, if the thickness is too thin, the inorganic oxide fine particles and metal ions cannot be retained and may be separated from the functional film 2 . Moreover, there is also a possibility that durability may become low.
- the refractive index of the functional film 2 is preferably 1.1 to 1.5, more preferably 1.2 to 1.4.
- the photocatalyst fine particles are laminated between the dispersed inorganic oxide fine particles, and the voids formed by the laminated photocatalyst fine particles change the apparent refractive index of the functional film 2. can be reduced. Thereby, the reflectance can be reduced.
- the refractive index can be measured, for example, according to JIS B-7071-1:2015.
- the reflectance of the functional film 2 is preferably 0-10, more preferably 2-7. Reflectance can be measured, for example, based on JIS R-3106:2019.
- the method for forming the functional film 2 is not particularly limited, it can be formed, for example, as follows. First, a material forming the three-dimensional network structure described above, for example, a silicon alkoxide such as tetraethoxysilane is made into a solution under acidic conditions to generate a precursor liquid. In addition, a liquid containing the above-mentioned antibacterial metal ions, for example, a copper chloride aqueous solution, a dispersion containing inorganic oxide fine particles such as colloidal silica, and a dispersion containing photocatalyst fine particles such as titanium oxide, is added to the precursor. Mix to form a coating liquid for the functional membrane.
- a material forming the three-dimensional network structure described above for example, a silicon alkoxide such as tetraethoxysilane is made into a solution under acidic conditions to generate a precursor liquid.
- a liquid containing the above-mentioned antibacterial metal ions for example, a copper
- the coating liquid can be irradiated with ultraviolet rays in order to activate the photocatalyst fine particles.
- ultraviolet rays for example, ultraviolet rays of 5 to 50 W/m 2 can be irradiated for 1 to 24 hours.
- a coating liquid is applied to the first surface of the cleaned glass plate 1 .
- the coating method is not particularly limited, for example, a flow coating method, a spray coating method, a spin coating method, or the like can be employed.
- the applied coating liquid is dried in an oven or the like at a predetermined temperature (eg, 80 to 200 ° C.) to volatilize the alcohol content in the solution, for example, for hydrolysis and decomposition of the organic chain.
- a predetermined temperature for example, 200 to 500° C.
- the functional film 2 can be obtained.
- the inorganic oxide fine particles are generally formed in a single layer. , for example, 10% or less, preferably 7% or less, more preferably 5% or less.
- the visible light transmittance is preferably 80% or more, more preferably 90% or more.
- the haze ratio of the glass member 10 is, for example, 20% or less, further 15% or less, particularly 10% or less, and in some cases 0.1 to 8.0%, further 0.1 to 6.0%.
- the functional film 2 includes an inorganic oxide that forms three-dimensional network bonds, and inorganic oxide fine particles and photocatalyst fine particles held by the inorganic oxide. .
- voids are formed in the layered photocatalyst fine particles, thereby reducing the refractive index and, as a result, reducing the reflectance.
- the functional film of the present embodiment is generally formed of a single layer of inorganic oxide fine particles, it has a higher antireflection function than a functional film in which inorganic oxide fine particles are laminated over a plurality of layers.
- the filling rate of the binder and the photocatalyst fine particles in the layer close to the glass plate 1 is increased, and the voids are reduced.
- the apparent refractive index increases and the antireflection function deteriorates.
- the functional film can be made thinner, the cost can be reduced.
- the functional film 2 contains photocatalytic fine particles, it exhibits an antibacterial function and an antifouling function.
- the photocatalyst fine particles are laminated between one layer of inorganic oxide fine particles and exposed to the outside, the antibacterial function is easily exhibited.
- the portion of the photocatalyst fine particles exposed to the outside contains voids, it contributes to a decrease in the refractive index, thereby improving the low-reflection function. Therefore, the functional film 2 according to the present invention can achieve both a low-reflection function and an antibacterial function with a single film.
- the inorganic oxide serves as a binder that retains metal ions, when the functional film 2 contains antibacterial metal ions, the elution of the metal ions can be suppressed.
- the gaps between the inorganic oxide fine particles having a large average particle size are filled with the photocatalyst fine particles having a small average particle size. Elution of metal ions can be further suppressed.
- the photocatalyst fine particles are activated, antibacterial metal ions are reduced, and deposited on the surface of the photocatalyst fine particles. This further suppresses the elution of metal ions.
- Such an effect can be obtained not only when the finished functional film 2 is irradiated with light, but also when the coating liquid for the functional film 2 is irradiated with light as described above.
- the photocatalyst fine particles and the metal ions or ion complexes are electrostatically bound, the elution of the metal ions is further suppressed.
- the photocatalytic fine particles have an antibacterial effect, in addition to the antibacterial metal ions, the antibacterial performance can be further improved.
- a glass plate is used as the substrate of the present invention in the above embodiment, a resin substrate other than the glass plate can also be used.
- Examples of the present invention will be described below. However, the present invention is not limited to the following examples.
- (1) Preparation of Examples A float glass plate having a size of 50 mm x 50 mm and a thickness of 1.1 mm was prepared, and its surface was subjected to alkaline ultrasonic cleaning. Next, for Examples 1 to 12, coating liquids for functional films having the compositions shown below were prepared. The concentration of solids in the coating liquids of Examples 1-5 was 5%, the concentration of solids in the coating liquids of Examples 6-11 was 7%, and the solid content in the coating liquids of Examples 12-14 was concentration was 4%. Note that only Example 14 contains copper ions. Further, Table 4 shows the details of Concentrate Total in Tables 1 to 3. All units are g.
- STS-01 in Tables 1 to 3 is a TiO 2 fine particle dispersion available from Ishihara Sangyo Co., Ltd.
- PL-7 in Table 4 is a SiO 2 fine particle dispersion available from Fuso Chemical Industry Co., Ltd.
- the coating liquids of Examples 1 to 14 were applied to the surface of the glass plate by spin coating, and then heated in an oven at 300°C for 30 minutes.
- glass members according to Examples 1 to 15 were obtained.
- the film thickness of the functional film in each example was about 100 nm.
- the composition of the functional film of the completed glass member is as follows.
- the unit is % by mass.
- Examples 1 to 5 mainly vary the content of TiO 2 fine particles.
- Examples 6 to 11 the content of TiO 2 fine particles was constant, and the content of SiO 2 fine particles and SiO 2 binder was varied.
- the higher the content of TiO 2 fine particles the higher the visible light reflectance at wavelengths of 600 nm or less, and the lower the reflectance at wavelengths of 600 nm or more. That is, the higher the content of TiO2 fine particles, the lower the low-reflection function in the wavelength region shorter than 600 nm due to the influence of the refractive index of TiO2 . improves. This is because even if the size of the air gap is the same, the influence of the air gap differs depending on the wavelength.
- the reflectance is lower than that of the glass plate without the antibacterial film in any wavelength range.
- the reflectance in the visible light range generally decreases as the amount of binder decreases.
- all of Examples 6 to 11 have a lower reflectance in the visible light range than the glass plate having no antibacterial film.
- Examples 6 and 7, in which the ratio of the content of the SiO2 fine particles to the total content of the SiO2 fine particles and the binder is greater than 0.4, or the content of the binder is less than 40%, is effective in the visible light region. It was found that the low reflectance performance was high.
- the reflectance in the visible light region to the infrared region of Example 14 containing copper ions is particularly low. It is considered that this is because copper ions absorb light.
- FIG. 6 shows the surface and cross section of the antibacterial film of Example 1 taken by SEM.
- silica fine particles with a large average particle size are dispersed on the surface of the antibacterial film, and titanium oxide fine particles with a small average particle size are stacked in the gaps between them.
- titanium oxide fine particles with a small average particle size are stacked in the gaps between them.
- Example 14 containing copper ions, which are antibacterial metal ions was 4.0 or higher.
- the antibacterial activities of Examples 1 to 13 were 3.5 or higher. If it is 2.0 or more, it is evaluated that there is antibacterial activity, so sufficient antibacterial performance could be confirmed in the glass members according to these examples.
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Abstract
Description
前記第1面に形成された機能膜と、
を備え、
前記機能膜は、
三次元ネットワーク結合を構成する金属酸化物を含有するバインダと、
前記バインダにより保持され、一層で分散される金属酸化物微粒子と、
前記金属酸化物微粒子の間に配置される光触媒微粒子と、
を含有する、積層体。
前記光触媒微粒子は、酸化チタンにより形成されている、項1または2に記載の積層体。
ガラス板1は、例えば、汎用のソーダライムガラス、ホウケイ酸ガラス、アルミノシリケートガラス、無アルカリガラス等その他のガラスにより形成することができる。また、ガラス板1は、フロート法により成形することができる。この製法によると平滑な表面を有するガラス板1を得ることができる。但し、ガラス板10は、主面に凹凸を有していてもよく、例えば型板ガラスであってもよい。型板ガラスは、ロールアウト法と呼ばれる製法により成形することができる。この製法による型板ガラスは、通常、ガラス板の主面に沿った一方向について周期的な凹凸を有する。
SiO2 65~80%
Al2O3 0~16%
MgO 0~20%
CaO 0~20%
Na2O 10~20%
K2O 0~5%
(SiO2)
SiO2は、ガラス板1を構成する主要成分であり、その含有率が低すぎるとガラスの耐水性などの化学的耐久性および耐熱性が低下する。他方、SiO2の含有率が高すぎると、高温でのガラス板1の粘性が高くなり、溶解および成形が困難になる。したがって、SiO2の含有率は、66~72mol%の範囲が適切であり、67~70mol%が好ましい。
Al2O3はガラス板1の耐水性などの化学的耐久性を向上させ、さらにガラス中のアルカリ金属イオンの移動を容易にすることにより化学強化後の表面圧縮応力を高め、かつ、応力層深さを深くするための成分である。他方、Al2O3の含有率が高すぎると、ガラス融液の粘度を増加させ、T2、T4を増加させると共にガラス融液の清澄性が悪化し高品質なガラス板を製造することが難しくなる。
MgOはガラスの溶解性を向上させる必須の成分である。この効果を十分に得る観点から、このガラス板1ではMgOが添加されていることが好ましい。また、MgOの含有率が8mol%を下回ると、化学強化後の表面圧縮応力が低下し、応力層深さが浅くなる傾向にある。一方、適量を越えて含有率を増やすと、化学強化により得られる強化性能が低下し、特に表面圧縮応力層の深さが急激に浅くなる。この悪影響は、アルカリ土類金属酸化物の中でMgOが最も少ないが、このガラス板1においては、MgOの含有率は15mol%以下である。また、MgOの含有率が高いと、T2、T4を増加させると共にガラス融液の清澄性が悪化し高品質なガラス板を製造することが難しくなる。
CaOは、高温での粘性を低下させる効果を有するが、適度な範囲を超えて含有率が高すぎると、ガラス板1が失透しやすくなるとともに、ガラス板1におけるナトリウムイオンの移動が阻害されてしまう。CaOを含有しない場合に化学強化後の表面圧縮応力が低下する傾向にある。一方、8mol%を超えてCaOを含有すると、化学強化後の表面圧縮応力が顕著に低下し、圧縮応力層深さが顕著に浅くなるとともに、ガラス板1が失透しやすくなる。
SrO、BaOは、ガラス板1の粘性を大きく低下させ、少量の含有では液相温度TLを低下させる効果がCaOより顕著である。しかし、SrO、BaOは、ごく少量の添加であっても、ガラス板1におけるナトリウムイオンの移動を顕著に妨げ、表面圧縮応力を大きく低下させ、かつ、圧縮応力層の深さがかなり浅くなる。
Na2Oは、ナトリウムイオンがカリウムイオンと置換されることにより、表面圧縮応力を大きくし、表面圧縮応力層の深さを深くするための成分である。しかし、適量を超えて含有率を増やすと、化学強化処理でのイオン交換による表面圧縮応力の発生を、化学強化処理中の応力緩和が上回るようになり、結果として表面圧縮応力が低下する傾向にある。
K2Oは、Na2Oと同様、ガラスの溶解性を向上させる成分である。また、K2Oの含有率が低い範囲では、化学強化におけるイオン交換速度が増加し、表面圧縮応力層の深さが深くなる一方で、ガラス板1の液相温度TLを低下させる。したがってK2Oは低い含有率で含有させることが好ましい。
Li2Oは、少量含有されるだけであっても圧縮応力層の深さを著しく低下させる。また、Li2Oを含むガラス部材を硝酸カリウム単独の溶融塩で化学強化処理する場合、Li2Oを含まないガラス部材の場合と比較して、その溶融塩が劣化する速度が著しく速い。具体的には、同じ溶融塩で繰り返し化学強化処理を行なう場合に、より少ない回数でガラス表面に形成される表面圧縮応力が低下する。したがって、本実施形態のガラス板1においては、1mol%以下のLi2Oを含有してもよいが、実質的にLi2Oを含有しない方が好ましい。
B2O3は、ガラス板1の粘性を下げ、溶解性を改善する成分である。しかし、B2O3の含有率が高すぎると、ガラス板1が分相しやすくなり、ガラス板1の耐水性が低下する。また、B2O3とアルカリ金属酸化物とが形成する化合物が揮発してガラス溶解室の耐火物を損傷するおそれが生じる。さらに、B2O3の含有は化学強化における圧縮応力層の深さを浅くしてしまう。したがって、B2O3の含有率は0.5mol%以下が適切である。本発明では、B2O3を実質的に含有しないガラス板1であることがより好ましい。
通常Feは、Fe2+又はFe3+の状態でガラス中に存在し、着色剤として作用する。Fe3+はガラスの紫外線吸収性能を高める成分であり、Fe2+は熱線吸収性能を高める成分である。ガラス板1をディスプレイのカバーガラスとして用いる場合、着色が目立たないことが求められるため、Feの含有率は少ない方が好ましい。しかし、Feは工業原料により不可避的に混入することが多い。したがって、Fe2O3に換算した酸化鉄の含有率は、ガラス板1全体を100質量%として示して0.15質量%以下とすることがよく、0.1質量%以下であることがより好ましく、更に好ましくは0.02質量%以下である。
TiO2は、ガラス板1の粘性を下げると同時に、化学強化による表面圧縮応力を高める成分であるが、ガラス板1に黄色の着色を与えることがある。したがって、TiO2の含有率は0~0.2質量%が適切である。また、通常用いられる工業原料により不可避的に混入し、ガラス板1において0.05質量%程度含有されることがある。この程度の含有率であれば、ガラスに着色を与えることはないので、本実施形態のガラス板1に含まれてもよい。
ZrO2は、とくにフロート法でガラス板を製造する際に、ガラスの溶融窯を構成する耐火レンガからガラス板1に混入することがあり、その含有率は0.01質量%程度であることが知られている。一方、ZrO2はガラスの耐水性を向上させ、また、化学強化による表面圧縮応力を高める成分である。しかし、ZrO2の高い含有率は、作業温度T4の上昇や液相温度TLの急激な上昇を引き起こすことがあり、またフロート法によるガラス板の製造においては、析出したZrを含む結晶が製造されたガラス中に異物として残留しやすい。したがって、ZrO2の含有率は0~0.1質量%が適切である。
フロート法においては、ボウ硝(Na2SO4)など硫酸塩が清澄剤として汎用される。硫酸塩は溶融ガラス中で分解してガス成分を生じ、これによりガラス融液の脱泡が促進されるが、ガス成分の一部はSO3としてガラス板1中に溶解し残留する。本発明のガラス板1においては、SO3は0~0.3質量%であることが好ましい。
CeO2は清澄剤として使用される。CeO2により溶融ガラス中でO2ガスが生じるので、CeO2は脱泡に寄与する。一方、CeO2が多すぎると、ガラスが黄色に着色してしまう。そのため、CeO2の含有量は、0~0.5質量%が好ましく、0~0.3質量%がより好ましく、0~0.1質量%がさらに好ましい。
フロート法により成形されたガラス板において、成型時にスズ浴に触れた面はスズ浴からスズが拡散し、そのスズがSnO2として存在することが知られている。また、ガラス原料に混合させたSnO2は、脱泡に寄与する。本発明のガラス板1においては、SnO2は0~0.3質量%であることが好ましい。
本実施形態によるガラス板1は、上記に列挙した各成分から実質的に構成されていることが好ましい。ただし、本実施形態によるガラス板1は、上記に列記した成分以外の成分を、好ましくは各成分の含有率が0.1質量%未満となる範囲で含有していてもよい。
上記組成より、本実施形態では、ガラス板1の密度を2.53g・cm-3以下、さらには2.51g・cm-3以下、場合によっては2.50g・cm-3以下にまで減少させることができる。
イオン交換を伴う化学強化を行うと、ガラス基板に反りが生じることがある。この反りを抑制するためには、ガラス板1の弾性率は高いことが好ましい。本発明によれば、ガラス板1の弾性率(ヤング率:E)を70GPa以上、さらには72GPa以上にまで増加させることができる。
(化学強化の条件と圧縮応力層)
ナトリウムを含むガラス板1を、ナトリウムイオンよりもイオン半径の大きい一価の陽イオン、好ましくはカリウムイオン、を含む溶融塩に接触させ、ガラス板1中のナトリウムイオンを上記の一価の陽イオンによって置換するイオン交換処理を行うことにより、本発明によるガラス板1の化学強化を実施することができる。これによって、表面に圧縮応力が付与された圧縮応力層が形成される。
次に、機能膜2について、図2を参照しつつ説明する。図2は機能膜の表面付近の概略を示す拡大断面図である。機能膜2は、三次元ネットワーク結合を構成する無機酸化物と、この無機酸化物に保持される無機酸化物微粒子と、この無機酸化物に保持される光触媒微粒子と、を備えている。また、必要に応じて、抗菌性の金属イオンを添加することもできる。以下、これらについて説明する。
無機酸化物は、無機酸化物微粒子及び金属イオンを保持するバインダとしての役割を果たす。無機酸化物としては、例えば、Siの酸化物である酸化シリコンを含み、酸化シリコンを主成分とすることが好ましい。酸化シリコンを主成分とすることで、膜の屈折率を低下させ、膜の反射率を抑制することに適している。機能膜には、酸化シリコン以外の成分を含んでいてもよく、酸化シリコンを部分的に含む成分を含んでいてもよい。
RnSiY4-n (1)
Rは、アルキル基、ビニル基、エポキシ基、スチリル基、メタクリロイル基及びアクリロイル基から選ばれる少なくとも1種を含む有機基である。Yは、アルコキシ基、アセトキシ基、アルケニルオキシ基及びアミノ基から選ばれる少なくとも1種である加水分解可能な有機基、又はハロゲン原子である。ハロゲン原子は、好ましくはClである。nは、0から3までの整数であり、好ましくは0又は1である。
機能膜2は、無機酸化物の少なくとも一部として、無機酸化物微粒子をさらに含んでいる。図2に示すように、無機酸化物微粒子は、ガラス1板上に概ね一層が分散されている。無機酸化物微粒子を構成する無機酸化物は、例えば、Si、Al、Ti、Zr、Ta、Nb、Nd、La、Ce及びSnから選ばれる少なくとも1種の元素の酸化物である。無機酸化物微粒子を複数種含有させることもできる。例えば、平均粒径が相違する複数の無機酸化物微粒子を含有させることができる。平均粒径の大きい無機酸化物微粒子としては、例えば、シリカ微粒子を採用することができる。シリカ微粒子は、例えば、コロイダルシリカを添加することにより機能膜2に導入できる。無機酸化物微粒子は、機能膜2に加えられた応力を、機能膜2を支持するガラス板1に伝達する作用に優れ、硬度も高い。したがって、無機酸化物微粒子の添加は、機能膜2の耐摩耗性を向上させる観点から有利である。無機酸化物微粒子は、機能膜2を形成するための塗工液に、予め形成した無機酸化物微粒子を添加することにより、機能膜2に供給することができる。
図2に示すように、無機酸化物微粒子は、隣接する無機酸化物微粒子の間に複数層に亘って積層されている。光触媒微粒子としては、例えば、酸化チタン(TiO2)、酸化セリウム(CeO2)等の微粒子を用いることができる。光触媒微粒子の平均粒径は、上述したシリカ微粒子等の無機酸化物微粒子の平均粒径よりも小さく、例えば、1~50nmであることが好ましく、25~30nmであることがさらに好ましい。光触媒微粒子の含有量は、機能膜2において、35~70質量%であることが好ましく、40~60質量%であることが好ましい。
金属イオンは、抗菌性を有するものであり、1価または2価の銅イオン、銀イオンなどで形成することができる。機能膜2の金属イオンの含有量は、例えば、機能膜2の1~30質量%であることが好ましく、3~15質量%であることがさらに好ましい。
機能膜2の厚みは、例えば、10~200nmであることが好ましく、50~150nmであることがさらに好ましい。厚みが厚すぎると、ヘイズ率が高くなったり、過度の着色が生じるおそれがある。一方、厚みが薄すぎると、無機酸化物微粒子や金属イオンを保持できず、機能膜2から離脱するおそれがある。また、耐久性が低くなるおそれもある。
機能膜2の屈折率は、1.1~1.5であることが好ましく、1.2~1.4であることがさらに好ましい。上記のように、本発明に係る機能膜2では、分散した無機酸化物微粒子の間に光触媒微粒子が積層され、積層された光触媒微粒子によって形成される空隙によって、機能膜2の見かけの屈折率を低減することができる。これにより、反射率を低減することができる。屈折率は、例えば、JIS B-7071-1:2015に準じた方法に基づいて測定することができる。
機能膜2の形成方法は、特には限定されないが、例えば、以下のように形成することができる。まず、上述した三次元ネットワーク構造を構成する材料、例えば、テトラエトキシシラン等のシリコンアルコキシドを酸性条件下で溶液とし、前駆体液を生成する。また、上述した抗菌性の金属イオンを含む液、例えば、塩化銅水溶液、コロイダルシリカ等の無機酸化物微粒子を含有する分散液、及び酸化チタン等の光触媒微粒子を含有する分散液を、前駆体に混合し、機能膜用のコーティング液を生成する。
なお、上記のように、完成後の機能膜では、無機酸化物微粒子が概ね一層形成されているが、そのためには、コーティング液を薄く塗布したり、あるいは、コーティング液中の固形分の濃度を、例えば、10%以下、好ましくは7%以下、さらに好ましくは5%以下にすればよい。
ガラス部材10の光学特性としては、例えば、可視光透過率が80%以上であることが好ましく、90%以上であることがさらに好ましい。また、ガラス部材10のヘイズ率は、例えば20%以下、さらに15%以下、特に10%以下であり、場合によっては0.1~8.0%、さらに0.1~6.0%であってもよい。
(1)本実施形態に係るガラス部材10では、機能膜2が、三次元ネットワーク結合を構成する無機酸化物と、無機酸化物に保持される無機酸化物微粒子及び光触媒微粒子と、を備えている。上記のように、積層された光触媒微粒子には空隙が形成されるため、これによって屈折率を低減し、その結果、反射率を低減することができる。特に、本実施形態の機能膜は、無機酸化物微粒子が概ね一層で形成されているため、複数層に亘って無機酸化物微粒子が積層されている機能膜と比べ反射抑制機能が高い。これに対して、無機酸化物微粒子が複数層に亘って形成されていると、ガラス板1に近い層でのバインダ及び光触媒微粒子の充填率が高くなり、空隙が少なくなる。そのため、見かけ上の屈折率が高くなり、反射抑制機能が低下する。また、機能膜を薄くできるため、コストも低減することができる。
以上、本発明の一実施形態について説明したが、本発明はこれに限定されるものではなく、その趣旨を逸脱しない限りにおいて種々の変更が可能である。なお、以下の変形例は、適宜組み合わせることができる。
(1)実施例の準備
50mmx50mm、厚みが1.1mmのフロートガラス板を準備し、その表面に対し、アルカリ超音波洗浄を行った。次に、実施例1~12について、以下に示す組成の機能膜用のコーティング液を調製した。実施例1~5のコーティング液中の固形分の濃度は5%とし、実施例6~11のコーティング液中の固形分の濃度は7%とし、実施例12~14のコーティング液中の固形分の濃度は4%とした。なお、実施例14のみ、銅イオンを含有させている。また、表1~表3中のConcentrate Totalについては、表4に詳細を示している。いずれも単位は、gである。
実施例1~14のガラス部材に対し、以下の試験を行った。
JIS R-3106:2019に基づいて反射率を測定した。また、比較対象として機能膜が形成されていないガラス板を用いた。結果は、図3~図5に示すとおりである。
実施例1~10のガラス部材を高温高湿環境(85℃、85%RH)で48時間、立て掛けて放置した。その後、ブラックライトUV1mW/cm2を照射し、滴下した水滴の接触角が5度以下になるまでの時間を測定した。結果は以下の通りである。
抗菌性の評価を、以下の通り、JIS R1702:2020(フィルム密着法)に基づいて行った。
・試験細菌:E.Coli(大腸菌 NBRC3972)
・試料形態:上記ガラス部材
・作用時間:8時間
・UV照射(波長360nm):0.25mW/cm2
・抗菌活性値(R)の算出:R=(Ut-U0)-(At-U0)=Ut-At
U0:ガラス板の接種直後の生菌数の対数値の平均値
Ut:ガラス板の8時間後の生菌数の対数値の平均値
At:ガラス部材の8時間後の生菌数の対数値の平均値
・作用条件:温度35℃、湿度90%以上(JIS準拠)
・密着フィルム:40mm×40mmのPPフィルム(JIS基準)
・試験菌液の摂取量:0.2ml
・試験菌液の生菌数:1.1×106
・生菌数測定:ガラス板の菌液接種直後および24時間培養後のガラス部材の生菌数を測定
2 機能膜
10 ガラス部材
100 物品
Claims (12)
- 第1面及び第2面を有する基板と、
前記第1面に形成された機能膜と、
を備え、
前記機能膜は、
三次元ネットワーク結合を構成する金属酸化物を含有するバインダと、
前記バインダにより保持され、一層で分散される無機酸化物微粒子と、
前記金属酸化物微粒子の間に配置される光触媒微粒子と、
を含有する、積層体。 - 前記機能膜に含有される、前記無機酸化物微粒子と前記バインダとの合計質量に対する前記金属酸化物微粒子の質量の割合が、0.4より大きい、請求項1に記載の積層体。
- 前記金属酸化物微粒子は、シリカにより形成され、
前記光触媒微粒子は、酸化チタンにより形成されている、請求項1または2に記載の積層体。 - 前記機能膜における、前記光触媒微粒子の含有量が35質量%以上である、請求項1から3のいずれかに記載の積層体。
- 前記機能膜における、前記金属酸化物微粒子の含有量が50質量%以下である、請求項1から4のいずれかに記載の積層体。
- 隣接する前記金属酸化物微粒子の間隔は、1μm未満である、請求項1から5のいずれかに記載の積層体。
- 前記光触媒微粒子は、前記金属酸化物微粒子の間で積層されている、請求項1から6のいずれかに記載の積層体。
- 前記金属酸化物微粒子の平均粒径は、前記光触媒微粒子の平均粒径の5倍以上である、
請求項1から7のいずれかに記載の積層体。 - 前記光触媒微粒子の屈折率は、前記基板よりも大きい、請求項1から8のいずれかに記載の積層体。
- 前記機能膜に、抗菌性の金属イオンが含有されている、請求項1から9のいずれかに記載に積層体。
- 前記金属イオンは、銅イオンである、請求項10に記載の積層体。
- 前記基板はガラス板である、請求項1から11のいずれかに記載の積層体。
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JP2010149321A (ja) * | 2008-12-24 | 2010-07-08 | Toto Ltd | 光触媒塗装体およびそのための光触媒コーティング液 |
WO2011021383A1 (ja) * | 2009-08-17 | 2011-02-24 | 日本板硝子株式会社 | 光触媒膜を備えたガラス物品 |
JP2013158683A (ja) | 2012-02-03 | 2013-08-19 | Nippon Sheet Glass Co Ltd | 光触媒膜を備えたガラス物品 |
WO2016121404A1 (ja) * | 2015-01-29 | 2016-08-04 | 日本板硝子株式会社 | 低反射コーティング付ガラス板、低反射コーティング付基材を製造する方法、及び低反射コーティング付基材の低反射コーティングを形成するためのコーティング液 |
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2010149321A (ja) * | 2008-12-24 | 2010-07-08 | Toto Ltd | 光触媒塗装体およびそのための光触媒コーティング液 |
WO2011021383A1 (ja) * | 2009-08-17 | 2011-02-24 | 日本板硝子株式会社 | 光触媒膜を備えたガラス物品 |
JP2013158683A (ja) | 2012-02-03 | 2013-08-19 | Nippon Sheet Glass Co Ltd | 光触媒膜を備えたガラス物品 |
WO2016121404A1 (ja) * | 2015-01-29 | 2016-08-04 | 日本板硝子株式会社 | 低反射コーティング付ガラス板、低反射コーティング付基材を製造する方法、及び低反射コーティング付基材の低反射コーティングを形成するためのコーティング液 |
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AR125617A1 (es) | 2023-08-02 |
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TW202304831A (zh) | 2023-02-01 |
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