CN108129032B - Transparent substrate with antifouling film - Google Patents
Transparent substrate with antifouling film Download PDFInfo
- Publication number
- CN108129032B CN108129032B CN201711338071.2A CN201711338071A CN108129032B CN 108129032 B CN108129032 B CN 108129032B CN 201711338071 A CN201711338071 A CN 201711338071A CN 108129032 B CN108129032 B CN 108129032B
- Authority
- CN
- China
- Prior art keywords
- transparent substrate
- film
- main surface
- antifouling film
- antifouling
- Prior art date
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- 239000000758 substrate Substances 0.000 title claims abstract description 161
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 117
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 43
- 239000011737 fluorine Substances 0.000 claims abstract description 42
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 41
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 39
- 230000003746 surface roughness Effects 0.000 claims abstract description 19
- 239000011521 glass Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 9
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 9
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 9
- 238000010030 laminating Methods 0.000 claims description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 150
- 239000010410 layer Substances 0.000 description 42
- 238000010438 heat treatment Methods 0.000 description 19
- 239000002904 solvent Substances 0.000 description 17
- 238000003426 chemical strengthening reaction Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000005871 repellent Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 235000002639 sodium chloride Nutrition 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- HJIMAFKWSKZMBK-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HJIMAFKWSKZMBK-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000005354 aluminosilicate glass Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000006059 cover glass Substances 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229960004624 perflexane Drugs 0.000 description 1
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000006058 strengthened glass Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 210000002268 wool Anatomy 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
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
-
- 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
- B32B17/10—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 synthetic resin
-
- 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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
-
- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
-
- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
-
- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/538—Roughness
-
- 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
- C03C2217/77—Coatings having a rough surface
Landscapes
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Laminated Bodies (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Liquid Crystal (AREA)
- Optical Elements Other Than Lenses (AREA)
Abstract
The invention provides a transparent substrate with an antifouling film, which comprises: a transparent substrate having a first main surface and a second main surface opposite to the first main surface, the surface of the first main surface being subjected to antiglare processing; and a fluorine-containing organosilicon compound coating film which is an antifouling film provided on the first main surface side of the transparent substrate; the antifouling film has a surface roughness RMS of 0.05 to 0.25 [ mu ] m, and an average length RSm of a roughness curve element of 10 to 40 [ mu ] m.
Description
The application is a divisional application of patent applications with application dates 2014, 1 month and 22 days, international application numbers PCT/JP2014/051291 and Chinese application numbers 201480006778.1.
Technical Field
The present invention relates to a transparent substrate with an antifouling film.
Background
In recent years, various display devices such as a liquid crystal display have been used in many cases, particularly in portable devices and in-vehicle devices. In such a display device, a structure in which a transparent substrate is disposed has been conventionally adopted as a cover member. In addition, a substrate structure in which a touch panel with a transparent electrode is integrated with a cover glass is also known.
In such a display device, there are many opportunities for a human finger or the like to touch the surface of the transparent base, and grease or the like is likely to adhere to the surface of the transparent base when touched by the human finger or the like. Further, since the adhesion of grease or the like affects the visibility, a transparent substrate is used which is subjected to an antifouling treatment on the surface thereof.
As a transparent substrate having a surface subjected to an antifouling treatment, for example, patent document 1 discloses a water-repellent glass having a water-repellent layer provided on a surface of a glass substrate having an uneven shape.
In addition, in the water-repellent glass provided with a water-repellent layer, since the water-repellent layer has a weak adhesive force with glass and it is difficult to maintain the water-repellent performance, a method of shaping the surface shape of a glass substrate into a predetermined shape has been studied in order to improve the durability (for example, patent document 2).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. H07-126041
Patent document 2: japanese laid-open patent publication No. 11-171594
Disclosure of Invention
Problems to be solved by the invention
However, the water repellent glass of patent document 2 is developed for the purpose of windshield glass, window glass sheet, and the like, and is not intended to be used as a transparent substrate of a display device or the like.
Therefore, when the water-repellent glass is used as a cover member of a display device such as a liquid crystal display or a cover glass integrated with a transparent electrode of a touch panel, there is a problem that the visibility of a display portion is lowered by reflecting ambient light because the water-repellent glass hardly has an antiglare property.
Further, as described above, the water-repellent glass of patent document 2 is intended to be used for a portion such as a window glass which is less likely to be touched by a human hand, and therefore, when used as a cover member which is likely to be touched by a human hand at a high frequency like a display device or a substrate integrated with a touch panel, durability is insufficient.
In view of the problems of the prior art, an object of the present invention is to provide a transparent substrate with an antifouling film having an antiglare property and improved durability of the antifouling film.
Means for solving the problems
In order to solve the above problems, the present invention provides a transparent substrate with an antifouling film, comprising:
a transparent substrate having a first main surface and a second main surface opposite to the first main surface, the surface of the first main surface being subjected to antiglare processing; and
a fluorine-containing organosilicon compound coating film which is an antifouling film provided on the first main surface side of the transparent substrate;
the antifouling film has a surface roughness RMS of 0.05 to 0.25 [ mu ] m, and an average length RSm of a roughness curve element of 10 to 40 [ mu ] m.
Effects of the invention
The present invention can provide a transparent substrate with an antifouling film, which has an antiglare property and simultaneously improves the durability of the antifouling film.
Drawings
Fig. 1 is an explanatory view of the structure of a transparent substrate with an antifouling film according to embodiment 1 of the present invention.
Fig. 2 is an explanatory view of the structure of the transparent substrate with the antifouling film according to embodiment 2 of the present invention.
Detailed Description
The present invention is not limited to the embodiments described below, and various modifications and substitutions may be made to the embodiments described below without departing from the scope of the present invention.
Embodiment 1
In this embodiment, a transparent substrate with an antifouling film of the present invention will be described.
The transparent substrate with an antifouling film of the present embodiment has a transparent substrate having a first main surface and a second main surface opposite to the first main surface, and an antiglare treatment is performed on a surface of the first main surface, and a fluorine-containing organosilicon compound coating film provided on the first main surface side of the transparent substrate. The transparent substrate with the antifouling film is characterized in that: the surface roughness RMS of the antifouling film is 0.05 μm or more and 0.25 μm or less, and the average length RSm of the roughness curve element is 10 μm or more and 40 μm or less.
The transparent substrate with an antifouling film according to the present embodiment will be described with reference to fig. 1. Fig. 1 schematically shows a cross-sectional view of a transparent substrate with an antifouling film according to the present embodiment, and has a structure in which an antifouling film 12 is disposed on a first main surface side of a transparent substrate 11. The following describes the respective members constituting the transparent substrate with the antifouling film.
First, the material of the transparent substrate 11 is not particularly limited, and various transparent substrates that transmit at least visible light can be used. Examples thereof include: various materials such as plastic substrates and glass substrates. Among them, the transparent substrate is preferably a glass substrate from the viewpoint of transparency, strength, and the like. In this case, the kind of glass is not particularly limited, and various glasses such as alkali-free glass, soda-lime glass, and aluminosilicate glass can be used. Among them, soda-lime glass is preferably used from the viewpoint of adhesion to a layer (film) provided thereon.
When the transparent substrate 11 is a glass substrate, a strengthened glass substrate (for example, "dragonttail" (registered trademark)) obtained by subjecting aluminosilicate glass to chemical strengthening treatment is preferably used from the viewpoint of the strength of the transparent substrate itself.
The chemical strengthening treatment is a treatment of replacing alkali ions (for example, sodium ions) having a small ionic radius on the glass surface with alkali ions (for example, potassium ions) having a large ionic radius. For example, glass containing sodium ions can be chemically strengthened by treating it with a molten salt containing potassium ions. The composition of the compressive stress layer on the surface of the glass substrate after the chemical strengthening treatment is slightly different from the composition before the chemical strengthening treatment, but the composition of the deep layer portion of the substrate is substantially the same as the composition before the chemical strengthening treatment.
The conditions for chemical strengthening are not particularly limited, and may be selected according to the kind of glass to be chemically strengthened, the desired degree of chemical strengthening, and the like.
The molten salt used for the chemical strengthening treatment may be selected according to the glass substrate to be chemically strengthened. Examples thereof include: alkali metal sulfates and alkali metal chlorides such as potassium nitrate, sodium sulfate, potassium sulfate, sodium chloride and potassium chloride, and the like. These molten salts may be used alone or in combination of two or more.
The heating temperature of the molten salt is preferably 350 ℃ or higher, and more preferably 380 ℃ or higher. Further, it is preferably 500 ℃ or lower, more preferably 480 ℃ or lower.
By setting the heating temperature of the molten salt to 350 ℃ or higher, it is possible to prevent the chemical strengthening from becoming difficult due to the decrease in the ion exchange rate. Further, decomposition and deterioration of the molten salt can be suppressed by setting the temperature to 500 ℃ or lower.
In order to impart sufficient compressive stress, the glass substrate is preferably brought into contact with the molten salt for 1 hour or more, more preferably 2 hours or more. Further, in the case of ion exchange for a long time, productivity is lowered, and the value of compressive stress is lowered by relaxation, and therefore, it is preferably 24 hours or less, more preferably 20 hours or less.
The shape of the transparent substrate is not particularly limited, and transparent substrates having various shapes can be used.
The transparent substrate 11 has the first main surface 11A and the second main surface 11B opposed thereto as described above. Further, an antiglare process for forming a desired uneven shape is performed on the first main surface 11A. In this case, the surface roughness RMS of the first main surface 11A is preferably 0.05 μm or more and 0.25 μm or less, and the average length RSm of the roughness curve element of the first main surface 11A is preferably 10 μm or more and 40 μm or less. By setting the surface roughness RMS and the average length RSm of the roughness curve element of the antifouling film, which will be described later, to be within desired ranges.
Here, the surface roughness RMS means an average depth of the concavities and convexities from a reference surface (here, a substrate surface before surface treatment). It is also referred to as root mean square roughness, and may be represented by Rq. The average length RSm of the roughness curve element is a length obtained by averaging lengths on a reference surface on which one-cycle unevenness appears, among roughness curves included in the reference length obtained on the reference surface. The surface roughness RMS (μm) and the average length RSm of the roughness curve element can be measured by a method based on the method specified in JIS B0601 (2001).
This is a result of studies conducted by the inventors of the present invention to improve the durability of the antifouling film on the transparent substrate with an antifouling film, and it has been found that, by providing the surface characteristics of the first main surface 11A with the above characteristics, the durability of the antifouling film is improved in particular compared with the conventional transparent substrate with an antifouling film in addition to the antiglare characteristic.
The antifouling film is formed on the first main surface side of the transparent substrate, and the antifouling film duplicates the surface shape of the transparent substrate, so that the surface of the antifouling film also has substantially the same surface roughness characteristics as the transparent substrate.
This means that, in comparison with the conventional transparent substrate having an anti-glare property with an RMS of more than 0.25 μm or an RSm of more than 40 μm, the first main surface 11A of the transparent substrate satisfies the above-mentioned requirements, and thus, the pitch between the concave portions is decreased and the area of the convex portions is increased in the fine irregularities on the first main surface of the transparent substrate. As described above, the surface of the antifouling film has the same surface shape.
When a finger or the like touches the stain-proofing film, which is the surface of the transparent substrate with the stain-proofing film, the area of the convex portion of the stain-proofing film in contact with the finger or the like is larger than that of the conventional transparent substrate with the stain-proofing film. Therefore, it is presumed that the force applied to the surface of the transparent substrate with the antifouling film (antifouling film) by fingers or the like is dispersed, and the pressure applied to the antifouling film can be reduced, whereby peeling and abrasion of the antifouling film can be suppressed.
It is estimated that the smaller the average length RSm of the roughness curve element, that is, the smaller the interval between the concave portions, the larger the contact area with the finger, and the durability is improved. However, in order to make RSm extremely small, it is necessary to perform etching treatment using a photomask, for example, and RSm can be preferably produced from the viewpoint of cost as long as it is 10 μm or more. Therefore, a transparent substrate satisfying the RSm range is preferably used for the surface on which the antifouling film is formed.
In the case of a transparent substrate having RMS and RSm within the above numerical range, the pitch of the recessed portions is within an appropriate range, and therefore, a transparent substrate having antiglare properties can be obtained.
The surface roughness RMS of the first main surface 11A is preferably 0.08 μm or more and 0.20 μm or less, and the average length RSm of the roughness curve element is preferably 15 μm or more and 35 μm or less. By satisfying these parameters, the durability of the antifouling film can be further improved.
The antiglare method for forming a transparent substrate having the above surface characteristics is not particularly limited, and a method of forming desired irregularities by subjecting the first main surface to a surface treatment may be used.
Specifically, there may be mentioned: a method of frosting the first main surface of the transparent substrate. The frosting treatment can be performed by, for example, immersing a transparent substrate as a treatment object in a mixed solution of hydrogen fluoride and ammonium fluoride to chemically surface-treat the immersion surface.
In addition to the above-mentioned chemical treatment method, for example, a method of blasting crystalline silica powder, silicon carbide powder, or the like with compressed air onto the surface of the transparent substrate; or a physical treatment method in which a brush to which crystalline silica powder, silicon carbide powder, or the like is attached is wetted with water and then polished with the brush.
In particular, in the method of performing the frosting treatment of chemically surface-treating the surface of the object to be treated with a reagent solution such as hydrogen fluoride, microcracks are not easily generated on the surface of the object to be treated, and a reduction in mechanical strength is not easily generated.
After the unevenness is formed in the above manner, the glass surface is generally chemically etched in order to modify the surface shape. This makes it possible to adjust the haze to a desired value by the etching amount, to remove cracks generated by sandblasting or the like, and to suppress glare.
As the etching, a method of immersing a transparent substrate as a treatment object in a solution containing hydrogen fluoride as a main component can be preferably used. The components other than hydrogen fluoride may include hydrochloric acid, nitric acid, citric acid, and the like. By containing these substances, a phenomenon that an alkali component incorporated into the glass reacts with hydrogen fluoride to cause a local precipitation reaction can be suppressed, and etching can be performed uniformly in a plane.
The second main surface 11B of the transparent substrate is not particularly limited in its characteristics, and may be processed so as to have the same surface roughness RMS and average length RSm of the roughness curve elements as those of the first main surface.
In addition, a transparent electrode for a touch panel may be formed on the second main surface 11B of the transparent substrate. In this way, the transparent electrode forming the touch panel and the transparent substrate with the antifouling film are integrated, so that further thinning and weight reduction can be achieved. In this case, it is preferable that the second main surface 11B is not subjected to the antiglare process similar to the first main surface 11A.
Further, as shown in fig. 1, an antifouling film 12 is formed on the first main surface 11A side of the transparent substrate 11. The antifouling film 12 may be composed of a fluorine-containing organosilicon compound.
Here, the fluorine-containing organosilicon compound will be described. The fluorine-containing organosilicon compound used in the present embodiment is not particularly limited as long as it is a fluorine-containing organosilicon compound that imparts stain-proofing properties, water repellency, and oil repellency.
Examples of such fluorine-containing organosilicon compounds include: a fluorine-containing organosilicon compound having one or more groups selected from the group consisting of a polyfluoropolyether group, a polyfluoroalkylene group and a polyfluoroalkyl group. The polyfluoropolyether group means a 2-valent group having a structure in which a polyfluoroalkylene group and an etheric oxygen atom are alternately bonded to each other.
Specific examples of the fluorine-containing organosilicon compound having at least one group selected from the group consisting of a polyfluoropolyether group, a polyfluoroalkylene group and a polyfluoroalkyl group include compounds represented by the following general formulae (I) to (V).
Wherein Rf is a C1-16 linear polyfluoroalkyl group (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, etc.) X is a hydrogen atom or a C1-5 lower alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, etc.), R1 is a hydrolyzable group (for example, amino, alkoxy, etc.) or a halogen atom (for example, fluorine, chlorine, bromine, iodine, etc.), m is an integer of 1-50, preferably 1-30, n is an integer of 0-2, preferably 1-2, and p is an integer of 1-10, preferably 1-8.
CqF2q+1CH2CH2Si(NH2)3(II)
Here, q is an integer of 1 or more, preferably an integer of 2 to 20.
Examples of the compound represented by the general formula (II) include: trifluoro (1,1,2, 2-tetrahydro) n-propylsilazane (n-CF)3CH2CH2Si(NH2)3) Heptafluoro (1,1,2, 2-tetrahydro) n-pentylsilazane (n-C)3F7CH2CH2Si(NH2)3) And the like.
Cg′F2q′+1CH2CH2Si(OCH3)3(III)
Here, q' is an integer of 1 or more, preferably an integer of 1 to 20.
Examples of the compound represented by the general formula (III) include: 2- (perfluorooctyl) ethyltrimethoxysilane (n-C)8F17CH2CH2Si(OCH3)3) And the like.
In the formula (IV), Rf2Is composed of- (OC)3F6)s-(OC2F4)t-(OCF2)uA 2-valent linear polyfluoropolyether group represented by (s, t and u are each independently an integer of 0 to 200), and R2、R3Each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, etc.). X2、X3Independently a hydrolyzable group (e.g., amino group, alkoxy group, acyloxy group, alkenyloxy group, isocyanate group, etc.) or a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), d, e independently an integer of 1 to 2, c, f independently an integer of 1 to 5 (preferably 1 to 2), a and b independently 2 or 3.
R of Compound (IV)f2Middle, s + t + u youPreferably 20 to 300, more preferably 25 to 100. In addition, as R2、R3More preferably methyl, ethyl, butyl. As a result of X2、X3The hydrolyzable group is more preferably an alkoxy group having 1 to 6 carbon atoms, and particularly preferably a methoxy group or an ethoxy group. In addition, a and b are each preferably 3.
F-(CF2)v-(OC3F6)w-(0C2F4)y-(OCF2)，(CH2)hO(CH2)i-Si(X4)3-k(R4)k(V)
In the formula (V), V is an integer of 1-3, w, y and z are each independently an integer of 0-200, h is 1 or 2, i is an integer of 2-20, and X is4Is a hydrolyzable group, R4Is a linear or branched hydrocarbon group having 1 to 22 carbon atoms, and k is an integer of 0 to 2. w + y + z is preferably 20 to 300, more preferably 25 to 100. In addition, i is preferably 2 to 10. X4The alkoxy group preferably has 1 to 6 carbon atoms, and more preferably a methoxy group or an ethoxy group. As R4Preferably, the alkyl group has 1 to 10 carbon atoms.
Further, as commercially available fluorine-containing organosilicon compounds having at least one group selected from the group consisting of a polyfluoropolyether group, a polyfluoroalkylene group and a polyfluoroalkyl group, KP-801 (trade name, manufactured by shin-Etsu chemical Co., Ltd.), KY178 (trade name, manufactured by shin-Etsu chemical Co., Ltd.), KY-130 (trade name, manufactured by shin-Etsu chemical Co., Ltd.), KY-185 (trade name, manufactured by shin-Etsu chemical Co., Ltd.), OPTOOL (registered trade name) DSX and OPTOOL AES (both trade name, manufactured by Daiko Co., Ltd.) can be preferably used.
In order to prevent deterioration due to reaction of the fluorine-containing organosilicon compound with moisture in the atmosphere, it is generally stored in a mixed state with a solvent such as a fluorine-containing solvent, but when the fluorine-containing organosilicon compound is directly supplied to a film-forming step in the case of containing such a solvent, the durability and the like of the obtained thin film may be adversely affected.
Therefore, in the present embodiment, it is preferable to use a fluorine-containing organosilicon compound that has been subjected to a solvent removal treatment in advance before heating in a heating vessel, or a fluorine-containing organosilicon compound that has not been diluted with a solvent (without adding a solvent). For example, the concentration of the solvent contained in the fluorine-containing organosilicon compound solution is preferably 1 mol% or less, and more preferably 0.2 mol% or less. It is particularly preferable to use a solvent-free fluorine-containing organosilicon compound.
The solvent used for storing the fluorine-containing organosilicon compound includes, for example: perfluorohexane, hexafluorom-xylene (C)6H4(CF3)2) Hydrofluoropolyether, HFE7200/7100 (trade name, manufactured by Sumitomo 3M Co., Ltd., HFE7200 is C4F9C2H5Presentation, HFE7100 by C4F9OCH3Represented), etc.
The treatment of removing the solvent (solvent) from the fluorine-containing organosilicon compound solution containing the fluorine-containing solvent can be performed, for example, by vacuum-evacuating a container in which the fluorine-containing organosilicon compound solution is placed.
The time for performing vacuum evacuation varies depending on the evacuation capability of the evacuation line, the vacuum pump, and the like, the amount of the solution, and the like, and is not limited, and may be, for example, about 10 hours or more.
The method for forming the antifouling film of the present embodiment is not particularly limited, and the film is preferably formed by vacuum deposition using the above-mentioned materials.
The solvent removal treatment may be performed by introducing the fluorine-containing organosilicon compound solution into a heating vessel of a film forming apparatus for forming an antifouling film, and then evacuating the heating vessel at room temperature before the temperature is raised. Alternatively, the solvent may be removed by an evaporator or the like before introduction into the heating vessel.
However, as described above, the fluorine-containing organosilicon compound containing a small amount of solvent or no solvent is more likely to be deteriorated by contact with the atmosphere than the case containing a solvent.
Therefore, it is preferable to use a container in which the container is sealed by replacing it with an inert gas such as nitrogen gas, and to shorten the time required for exposure to the atmosphere and contact with the atmosphere during handling.
Specifically, it is preferable to introduce the fluorine-containing organosilicon compound into the heating container of the film forming apparatus for forming the antifouling film immediately after the storage container is opened. After introduction, it is preferable to remove the atmosphere (air) contained in the heating container by evacuating the heating container or by replacing the heating container with an inert gas such as nitrogen or a rare gas. In order to introduce the liquid from the storage container (storage container) to the heating container of the present manufacturing apparatus without contacting the atmosphere, it is preferable that the storage container and the heating container are connected by a pipe with a valve, for example.
After the fluorine-containing organosilicon compound is introduced into the heating vessel, it is preferable that heating for film formation is started immediately after vacuum is formed in the vessel or the vessel is replaced with an inert gas.
In the description of the present embodiment, examples of using a fluorine-containing organosilicon compound in a solution or a stock solution as a method for forming an antifouling film are described, but the invention is not limited thereto. As other methods, for example: a commercially available method called vapor deposition particles (サーフクリア manufactured by キャノンオプトロン, for example) obtained by impregnating a porous metal (for example, tin or copper) or a fibrous metal (for example, stainless steel) with a predetermined amount of a fluorine-containing organosilicon compound are used. In this case, the antifouling film can be easily formed by using particles as a vapor deposition source in an amount according to the capacity of the vapor deposition apparatus and the desired film thickness.
As described above, since the antifouling film directly replicates the surface shape of the transparent substrate, the surface characteristics thereof are the same as the surface roughness RMS of the transparent substrate and the average length RSm of the roughness curve elements. Therefore, the surface roughness RMS is 0.05 μm or more and 0.25 μm or less, and the average length RSm of the roughness curve element is 10 μm or more and 40 μm or less. In particular, the surface roughness RMS is more preferably 0.08 μm or more and 0.20 μm or less, and the average length RSm of the roughness curve element is more preferably 15 μm or more and 35 μm or less.
In addition, an adhesive layer may be interposed between the transparent substrate and the antifouling film in order to improve the adhesion between the transparent substrate and the antifouling film. In the case of interposing the adhesive layer, the antifouling film may be formed on the first main surface of the transparent substrate in advance before forming the antifouling film. As the adhesion layer, a silicon oxide film is preferably used. The film thickness is 2nm to 50nm, preferably 5nm to 20 nm.
The above description has been made on each member of the transparent substrate with the antifouling film of the present embodiment, and the haze of the transparent substrate with the antifouling film of the present embodiment is preferably 2% or more and 30% or less. This is because, when the haze is 2% or more, the reflection of light can be remarkably suppressed by visual observation as compared with a substrate not subjected to the antiglare processing (see りこみ); if the amount is more than 30%, light is diffusely reflected, and the visibility of the display device is reduced when the display device is used as a cover member of the display device or a substrate integrated with a touch panel. The haze of the transparent substrate with the antifouling film of the present embodiment is preferably 15% or more and 27% or less.
It has been shown that: when the haze is within the above range, the transparent substrate with an antifouling film of the present embodiment has sufficient antiglare properties, and can be more preferably used as a cover member of a display device or the like or a substrate integrated with a touch panel.
According to the transparent substrate with an antifouling film of the present embodiment described above, a transparent substrate with an antifouling film having an antiglare property and improved durability of the antifouling film can be obtained.
[ 2 nd embodiment ]
In this embodiment, a configuration in which a low reflection film is further provided in embodiment 1 will be described. Other configurations are omitted here because they are as described in embodiment 1.
The low reflection film can suppress reflection of light on the surface of the transparent substrate with the anti-fouling film, and thus can further improve the anti-glare property. For example, when used as a cover member of a display device, the display device can suppress the reflection of ambient light and further improve the visibility of the display.
The material of the low reflection film is not particularly limited, and various materials can be used as long as they can suppress reflection. For example, the low reflection film may be formed by laminating a high refractive index layer and a low refractive index layer.
The high refractive index layer and the low refractive index layer may each include 1 layer, or may each include 2 or more layers. When the high refractive index layer and the low refractive index layer each include 2 or more layers, the high refractive index layer and the low refractive index layer are preferably alternately stacked.
In order to obtain sufficient antireflection performance, the low reflection film is preferably a laminate in which a plurality of films (layers) are laminated. For example, the laminate preferably has a total of 2 or more and 6 or less films stacked thereon, and more preferably has 2 or more and 4 or less films stacked thereon. The laminate herein is preferably a laminate obtained by laminating a high refractive index layer and a low refractive index layer as described above, and the total number of layers of the high refractive index layer and the low refractive index layer is preferably within the above range.
The material of the high refractive index layer and the low refractive index layer is not particularly limited, and may be selected in consideration of the required degree of antireflection, productivity, and the like. As the material constituting the high refractive index layer, for example, a material selected from niobium oxide (Nb) can be preferably used2O5) Titanium oxide (TiO)2) Zirconium oxide (ZrO)2) Silicon nitride (SiN) and tantalum oxide (Ta)2O5) More than one of (1). As a material constituting the low refractive index layer, silicon oxide (SiO) can be preferably used2)。
In particular, niobium oxide is preferably used as the high refractive index layer in view of productivity and the degree of refractive index. Therefore, the low reflection film is more preferably a laminate of a niobium oxide layer and a silicon oxide layer.
In the transparent substrate with an antifouling film of the present embodiment, the position where the low reflection film is provided is not particularly limited, and may be provided on the first main surface 11A and/or the second main surface 11B of the transparent substrate. Particularly preferably on the first main surface 11A of the transparent substrate. For example, as shown in fig. 2, the low reflection film 13 and the fluorine-containing organosilicon compound coating film 12 are more preferably formed on the surface (from the first main surface side) of the first main surface 11A of the transparent substrate 11 in this order.
The formation of the low reflection film 13 and the fluorine-containing organosilicon compound coating film (antifouling film) 12 laminated on the first main surface 11A of the transparent substrate as described above is preferable because peeling of the low reflection film 13 can be prevented and durability can be improved.
In addition, when an adhesive layer for improving the durability of the antifouling film is interposed, it is preferably interposed between the low reflection film and the antifouling film. In this case, the silicon oxide film is also a material preferably used, and as shown in the above example, in the case where the uppermost layer of the low reflection film is also silicon oxide, the low reflection film and the adhesion layer can be simultaneously achieved, and thus the silicon oxide film is a preferable configuration.
In fig. 2, the low reflection film 13 is formed by laminating 2 layers 131 and 132, but the invention is not limited to this form, and may be formed by further laminating a plurality of layers as described above.
The transparent substrate with an antifouling film according to the present embodiment also has a haze of preferably 2% to 30%, more preferably 15% to 27%, for the same reason as described in embodiment 1.
As described above, in the present embodiment, the transparent substrate with the anti-staining film having the low reflection film is explained, and the anti-glare property can be further improved by having this configuration. Therefore, the present invention can be more preferably used for applications requiring antiglare properties, such as a cover device of a display device and a substrate integrated with a touch panel.
Examples
The present invention will be described below by way of specific examples, but the present invention is not limited to these examples. Examples 1 to 4 are examples, and examples 5 to 7 are comparative examples.
(1) Evaluation method
The method for evaluating the characteristics of the transparent substrate with an antifouling film obtained in examples 1 to 7 below is described below.
(measurement of surface shape)
The surface shape of the antifouling film of the samples used in examples 1 to 7 after the antifouling film was formed was measured at a magnification of 50 times using a laser microscope (product name: VK-9700, manufactured by Keynes (キーエンス)). Then, from the obtained plane profile, values of surface roughness RMS and average length RSm of roughness curve elements were obtained based on JIS B0601 (2001).
In each example, the antifouling film and the low reflection film as the films are very thin films with respect to the thickness of the transparent substrate, and therefore the uneven structure on the surface substantially directly duplicates the surface shape of the transparent substrate. Therefore, the surface shape of the transparent base material (the surface on the side on which the antifouling film is formed) is considered to be the same.
(measurement of haze)
In the examples and comparative examples, the transmission haze was measured for the samples on which the antifouling films were formed. The haze measurement was carried out using a haze meter (model HZ-V3, manufactured by スガ testing machine Co., Ltd.).
(Friction durability (abrasion resistance) test)
For the samples after the antifouling films were formed in examples 1 to 7, the antifouling films of the samples were subjected to a friction durability test in the following procedure.
First, the antifouling films of examples 1 to 7 were subjected to a rubbing test in the following procedure.
A steel wool #0000 was attached to the surface of a flat metal indenter having a bottom surface of 10mm by 10mm to prepare a friction head for a friction sample.
Next, a rubbing test was performed by a flat abrasion tester 3 (model: PA-300A, manufactured by Darong Seiki Seisaku-Sho Ltd.) using the above rubbing head. Specifically, the indenter was first mounted on a wear tester so that the bottom surface of the indenter was in contact with the antifouling film surface of the sample, and a heavy object was loaded so that the load on the rubbing head was 1000g, and the indenter was slid back and forth at an average speed of 6400 mm/min and a single pass of 40 mm. The number of reciprocations 1 was counted as the number of rubs 1, and the test was performed such that the number of rubs was 1000.
Then, the water contact angle of the antifouling film was measured by the following procedure.
The water contact angle of the antifouling film was measured by dropping 1. mu.L of pure water onto the antifouling film using an automatic contact angle meter (model: DM-501, manufactured by Kyowa interface science Co., Ltd.) and measuring the contact angle. In the measurement, the water contact angle of each sample after the durability test was determined as the average value of 10 points on the surface of the antifouling film.
In this case, the water contact angle of 90 ° or more was evaluated as acceptable, and the water contact angle of 90 ° or less was evaluated as unacceptable.
(2) Experimental procedure
[ example 1]
A transparent substrate with an antifouling film was produced by the following procedure.
In this example, a glass substrate (hereinafter referred to as transparent substrate A) obtained by using a glass substrate (product name: "Dragnail" (registered trademark) manufactured by Asahi glass company Co., Ltd.) subjected to a chemical strengthening treatment and subjecting a first main surface of the glass substrate to a predetermined frosting treatment was used as the transparent substrate.
Then, an antifouling film was formed on the first main surface of the transparent substrate a by the following procedure.
First, a fluorine-containing organosilicon compound (product name: KY-185, product of shin-Etsu chemical Co., Ltd.) was introduced into a heating vessel as a vapor deposition material. Then, the interior of the heating vessel was degassed by a vacuum pump for 10 hours or more to remove the solvent in the solution, thereby producing a composition for forming a fluorine-containing organosilicon compound coating film.
Next, the heating vessel containing the above-mentioned composition for forming a fluorine-containing organosilicon compound film was heated to 270 ℃. After reaching 270 ℃, the state was maintained for 10 minutes until the temperature stabilized.
Then, the fluorine-containing organosilicon compound film-forming composition was supplied from a nozzle connected to a heating vessel containing the fluorine-containing organosilicon compound film-forming composition to the first main surface (frosted surface) of the transparent substrate a disposed in the vacuum chamber, and film formation was performed.
In the film formation, the film formation was carried out while measuring the film thickness by a crystal oscillator monitor installed in a vacuum chamber until the film thickness of the fluorine-containing organosilicon compound film formed on the transparent substrate A reached 10 nm.
When the fluorine-containing organosilicon compound film reached 10nm, the supply of the raw material from the nozzle was stopped, and the transparent substrate a on which the fluorine-containing organosilicon compound film was formed was taken out from the vacuum chamber.
The transparent substrate a on which the fluorine-containing organosilicon compound film was formed was taken out and set on a hot plate so that the film faced upward, and heat-treated at 150 ℃ for 60 minutes in the atmosphere.
The surface shape measurement, haze measurement, and friction durability test were performed on the samples obtained in the above manner. The results are shown in Table 1.
[ example 2]
An antifouling film was formed on the first main surface of the transparent substrate B in the same manner as in example 1, except that a glass substrate (product name: "dragontail" (registered trademark) manufactured by asahi glass corporation) subjected to chemical strengthening treatment was used as the transparent substrate, and the first main surface of the glass substrate was frosted. The obtained transparent substrate with the antifouling film was evaluated in the same manner as in example 1. The results are shown in Table 1.
[ example 3]
An antifouling film was formed on the first main surface of the transparent substrate C in the same manner as in example 1, except that a glass substrate (product name: "dragontail" (registered trademark) manufactured by asahi glass corporation) subjected to chemical strengthening treatment was used as the transparent substrate, and the first main surface of the glass substrate was frosted. The obtained transparent substrate with the antifouling film was evaluated in the same manner as in example 1. The results are shown in Table 1.
[ example 4]
A low reflection film was formed on the transparent substrate a in the following manner.
First, a mixed gas of 10 vol% of oxygen gas mixed with argon gas was introduced, and a niobium oxide target (NBO target, product name, manufactured by AGC ceramics) was used at a pressure of 0.3Pa, a frequency of 20kHz, and a power density of 3.8W/cm2And pulse sputtering was performed under a reverse pulse width of 5 μ s, thereby forming a high refractive index layer containing niobium oxide (niobia) having a thickness of 13nm on the first main surface of the transparent substrate a.
Then, a mixture of 40 vol% of oxygen gas and introduced argon gas was mixedWhile using a silicon target, the pressure is 0.3Pa, the frequency is 20kHz, and the power density is 3.8W/cm2And pulse sputtering was performed under a condition of a reverse pulse width of 5 microseconds and a pulse width of 5 microseconds, thereby forming a low refractive index layer containing silicon oxide (silica) having a thickness of 30nm on the high refractive index layer.
Next, a mixed gas of 10 vol% of oxygen gas mixed with argon gas was introduced, and a niobium oxide target (NBO target, product name, manufactured by AGC ceramics) was used at a pressure of 0.3Pa, a frequency of 20kHz, and a power density of 3.8W/cm2And pulse sputtering was performed under a reverse pulse width of 5 μ s, thereby forming a high refractive index layer containing niobium oxide (niobia) having a thickness of 110nm on the low refractive index layer.
Next, a mixed gas in which 40 vol% of oxygen was mixed with argon gas was introduced, and a silicon target was used at a pressure of 0.3Pa, a frequency of 20kHz, and a power density of 3.8W/cm2And pulse sputtering was performed under a condition of a reverse pulse width of 5 microseconds and a pulse width of 5 microseconds to form a low refractive index layer containing silicon oxide (silica) having a thickness of 90 nm.
In the above manner, a low reflection film in which a total of 4 layers of niobium oxide (niobia) and silicon oxide (silica) were stacked was formed.
Next, an antifouling film was formed on the low reflection film in the same manner as in example 1.
The obtained transparent substrate with the antifouling film was evaluated in the same manner as in example 1. The results are shown in Table 1.
[ example 5]
An antifouling film was formed on the first main surface of the transparent substrate D in the same manner as in example 1, except that a glass substrate (product name: "dragontail" (registered trademark) manufactured by asahi glass corporation) subjected to chemical strengthening treatment was used as the transparent substrate, and the first main surface of the glass substrate was frosted. The obtained transparent substrate with the antifouling film was evaluated in the same manner as in example 1. The results are shown in Table 1.
[ example 6]
An antifouling film was formed on the first main surface of the transparent substrate E in the same manner as in example 1, except that a glass substrate (product name: "dragontail" (registered trademark) manufactured by asahi glass corporation) subjected to chemical strengthening treatment was used as the transparent substrate, and the first main surface of the glass substrate was frosted. The obtained transparent substrate with the antifouling film was evaluated in the same manner as in example 1. The results are shown in Table 1.
[ example 7]
A low reflection film and an antifouling film were formed in the same manner as in example 4 except that the same transparent substrate D as in example 5 was used as the transparent substrate, and the obtained transparent substrate with an antifouling film was evaluated in the same manner as in example 1. The results are shown in Table 1.
[ Table 1]
From the results shown in table 1, it is understood that the water contact angles in the friction durability test were 90 ° or more for examples 1 to 4 satisfying the specification of the present invention, while the water contact angles were 80 ° or less for examples 5 to 7.
The antifouling film has water repellency, and the decrease in the water contact angle indicates peeling and abrasion of the antifouling film as described above. Therefore, in examples 5 to 7, the anti-fouling film was peeled off and abraded.
From these results, it was confirmed that examples 1 to 4 satisfying the requirements of the present invention have extremely high durability of the antifouling film as compared with examples 5 to 7 of comparative examples.
In examples 1 to 4, it was also confirmed from the haze value that the resin had an appropriate antiglare property.
Although the transparent substrate with the antifouling film has been described above with reference to the embodiments, examples, and the like, the present invention is not limited to the embodiments, examples, and the like. Various modifications and changes can be made within the scope of the gist of the present invention described in the claims.
The application claims priority of Japanese patent application No. 2013-015968 filed to the office on the basis of 30/1/2013, and the entire contents of the Japanese patent application No. 2013-015968 are incorporated into the international application.
Reference numerals
11 transparent substrate
12 antifouling film
13 Low reflection film
Claims (9)
1. A transparent substrate with an anti-fouling film, comprising:
a transparent substrate having a first major surface and a second major surface opposite to the first major surface, and
an antifouling film containing a fluorine-containing organosilicon compound provided on the first main surface side of the transparent substrate,
a surface roughness RMS of the first main surface of the transparent substrate is 0.05 μm or more and 0.25 μm or less, and an average length RSm of a roughness curve element of the first main surface of the transparent substrate is 10 μm or more and 40 μm or less,
the surface roughness RMS of the anti-fouling film is more than 0.05 μm and less than 0.25 μm, the average length RSm of the roughness curve element of the anti-fouling film is more than 10 μm and less than 40 μm, and
the antifouling film is formed by duplicating the surface shape of the first main surface of the transparent substrate.
2. The transparent substrate with an antifouling film according to claim 1, wherein the haze of the transparent substrate with an antifouling film is 2% or more and 30% or less.
3. The transparent substrate with an antifouling film according to claim 1 or 2, wherein the transparent substrate is a glass substrate.
4. The transparent substrate with a stain-proofing film according to claim 3,
the first main surface of the transparent substrate is subjected to a frosting process to form a concave-convex shape.
5. The transparent substrate with an antifouling film according to any one of claims 1,2 and 4, wherein a low-reflection film and the antifouling film are laminated in this order on the surface of the first main surface of the transparent substrate, and the low-reflection film is a laminate comprising a layer containing one or more selected from the group consisting of niobium oxide, titanium oxide, zirconium oxide, silicon nitride and tantalum oxide, and a silicon oxide layer.
6. The transparent substrate with an antifouling film according to any one of claims 1,2 and 4, wherein a low reflection film and the antifouling film are laminated in this order on the surface of the first main surface of the transparent substrate, the low reflection film is a laminate obtained by laminating a plurality of layers, and a total of 2 or more and 6 or less layers are laminated in the laminate.
7. The transparent substrate with a stain-proofing film according to any one of claims 1,2 and 4, wherein the surface roughness RMS of the stain-proofing film is 0.08 μm or more and 0.20 μm or less.
8. The transparent substrate with a stain-proofing film according to any one of claims 1,2 and 4, wherein the average length RSm of the roughness curve elements of the stain-proofing film is 15 μm or more and 35 μm or less.
9. A method for producing a transparent substrate with an antifouling film, comprising
A step of subjecting a first main surface of a transparent substrate having the first main surface and a second main surface opposite to the first main surface to a blast treatment, and
a step of forming an antifouling film containing a fluorine-containing organosilicon compound on the first main surface side of the transparent substrate,
wherein,
a surface roughness RMS of the first main surface of the transparent substrate is 0.05 μm or more and 0.25 μm or less, and an average length RSm of a roughness curve element of the first main surface of the transparent substrate is 10 μm or more and 40 μm or less,
the antifouling film is formed by duplicating the surface shape of the first main surface of the transparent substrate, and
the surface roughness RMS of the anti-fouling film is 0.05 μm to 0.25 μm, and the average length RSm of the roughness curve element of the anti-fouling film is 10 μm to 40 μm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-015968 | 2013-01-30 | ||
| JP2013015968 | 2013-01-30 | ||
| CN201480006778.1A CN104955783B (en) | 2013-01-30 | 2014-01-22 | Transparent base with anti-soil film |
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| CN201480006778.1A Division CN104955783B (en) | 2013-01-30 | 2014-01-22 | Transparent base with anti-soil film |
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| CN108129032A CN108129032A (en) | 2018-06-08 |
| CN108129032B true CN108129032B (en) | 2020-11-03 |
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| CN201480006778.1A Active CN104955783B (en) | 2013-01-30 | 2014-01-22 | Transparent base with anti-soil film |
| CN201711338071.2A Active CN108129032B (en) | 2013-01-30 | 2014-01-22 | Transparent substrate with antifouling film |
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| JP (2) | JP5839134B2 (en) |
| KR (2) | KR101916620B1 (en) |
| CN (2) | CN104955783B (en) |
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| CN104955783B (en) | 2018-01-26 |
| DE112014000613T5 (en) | 2015-10-29 |
| TWI596069B (en) | 2017-08-21 |
| JP2016052992A (en) | 2016-04-14 |
| KR101916620B1 (en) | 2018-11-07 |
| JP5839134B2 (en) | 2016-01-06 |
| WO2014119453A1 (en) | 2014-08-07 |
| JP6075435B2 (en) | 2017-02-08 |
| KR20150112972A (en) | 2015-10-07 |
| CN104955783A (en) | 2015-09-30 |
| KR101916507B1 (en) | 2018-11-07 |
| DE112014000613B4 (en) | 2019-05-29 |
| CN108129032A (en) | 2018-06-08 |
| JPWO2014119453A1 (en) | 2017-01-26 |
| KR20170137223A (en) | 2017-12-12 |
| TW201434775A (en) | 2014-09-16 |
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