CN117776546A - Anti-reflection glass - Google Patents
Anti-reflection glass Download PDFInfo
- Publication number
- CN117776546A CN117776546A CN202311262487.6A CN202311262487A CN117776546A CN 117776546 A CN117776546 A CN 117776546A CN 202311262487 A CN202311262487 A CN 202311262487A CN 117776546 A CN117776546 A CN 117776546A
- Authority
- CN
- China
- Prior art keywords
- refractive index
- glass
- antireflection
- index layer
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000011521 glass Substances 0.000 title claims abstract description 149
- 239000010410 layer Substances 0.000 claims abstract description 206
- 239000011241 protective layer Substances 0.000 claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 238000005452 bending Methods 0.000 claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims description 50
- 150000001875 compounds Chemical class 0.000 claims description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 229910044991 metal oxide Inorganic materials 0.000 claims description 23
- 150000004706 metal oxides Chemical class 0.000 claims description 22
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 claims description 20
- 238000012360 testing method Methods 0.000 claims description 18
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 239000013522 chelant Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000000413 hydrolysate Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000003426 chemical strengthening reaction Methods 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 4
- 230000003014 reinforcing effect Effects 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 62
- 239000003513 alkali Substances 0.000 description 38
- 239000002609 medium Substances 0.000 description 32
- 238000004140 cleaning Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
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- 238000000034 method Methods 0.000 description 13
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 8
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- -1 methoxy, ethoxy, propoxy Chemical group 0.000 description 8
- 238000005728 strengthening Methods 0.000 description 8
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- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000005341 toughened glass Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
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- 238000002834 transmittance Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
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- AMUZLNGQQFNPTQ-UHFFFAOYSA-J 3-oxohexanoate zirconium(4+) Chemical compound [Zr+4].CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O AMUZLNGQQFNPTQ-UHFFFAOYSA-J 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 125000005595 acetylacetonate group Chemical group 0.000 description 4
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- 229910021645 metal ion Inorganic materials 0.000 description 4
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
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- GSCOPSVHEGTJRH-UHFFFAOYSA-J [Ti+4].CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O Chemical compound [Ti+4].CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O GSCOPSVHEGTJRH-UHFFFAOYSA-J 0.000 description 3
- 239000011260 aqueous acid Substances 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
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- 150000002500 ions Chemical class 0.000 description 3
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- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
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- 150000003839 salts Chemical class 0.000 description 3
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- IUGGRDVCAVUMLN-UHFFFAOYSA-K [Zr+3].CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O Chemical compound [Zr+3].CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O IUGGRDVCAVUMLN-UHFFFAOYSA-K 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 239000005358 alkali aluminosilicate glass Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 2
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 2
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- 230000003667 anti-reflective effect Effects 0.000 description 2
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- CQKOAJVBVFKQOO-UHFFFAOYSA-L 3-oxohexanoate;zirconium(2+) Chemical compound [Zr+2].CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O CQKOAJVBVFKQOO-UHFFFAOYSA-L 0.000 description 1
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- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
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- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- FMGDJQPRGBQGAI-UHFFFAOYSA-K tribromoalumane hexahydrate Chemical compound O.O.O.O.O.O.[Al+3].[Br-].[Br-].[Br-] FMGDJQPRGBQGAI-UHFFFAOYSA-K 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Surface Treatment Of Glass (AREA)
- Laminated Bodies (AREA)
- Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
Abstract
An antireflection glass comprising, in order, a glass substrate, an antireflection film, and a protective layer, wherein the antireflection film comprises, in order from the glass substrate side: a medium refractive index layer having a refractive index of 1.67 to 1.87 and a film thickness of 35 to 120 nm; a high refractive index layer having a refractive index of 1.90 to 2.05 and a film thickness of 30 to 115 nm; and a low refractive index layer having a refractive index of 1.34 to 1.45 and a film thickness of 45 to 115nm, wherein the protective layer has a refractive index of 1.42 to 1.48 and a film thickness of 5 to 50nm, and the high refractive index layer is formed of a cured product of a curable composition containing a metal alkoxide oligomer, and the average light reflectance of both surfaces of the antireflection glass is 0.6% or less, and the protective layer and each layer of the antireflection film do not crack in bending in which the elongation of the glass surface is 5% or less.
Description
Technical Field
The present invention relates to an antireflection glass having a high antireflection capability, and is suitably used for manufacturing an antireflection reinforced glass subjected to bending.
Background
The reinforced glass with improved glass strength is widely used for window glass of automobiles and houses. Further, the present invention is also used for applications such as front protection panels for capacitive touch panels, displays for various mobile devices such as digital cameras and cellular phones.
In recent years, an integrated glass panel with a monitor called CID (Center Information Display ) which is also required to have aesthetic properties and high-quality feeling is required for an instrument panel for an automobile, and a method of connecting the instrument and the CID in a curved surface has been demanded. Since the glass panel is likely to be broken by accident or the like, the glass panel is necessarily required to be a tempered glass.
The dashboard for automobiles requires a high antireflection function as in the case of the protective panel and various displays. In order to provide an antireflection function, an antireflection film including a low refractive index layer may be formed on the surface of glass.
In order to improve the antireflection performance of the antireflection film, a high-performance multilayer antireflection film has been developed, such as a two-layer antireflection film having a high refractive index layer between a low refractive index layer and a glass substrate, and a three-layer antireflection film having a medium refractive index layer between a high refractive index layer and a glass substrate, instead of only one low refractive index layer (patent document 1).
However, in the case of the tempered glass having the above-described high-performance antireflection function, the following problems occur at the time of bending processing.
Prior art literature
Patent literature
Patent document 1: japanese patent application No. 2021-135870 (WO 2023/026670)
Disclosure of Invention
Problems to be solved by the invention
The high refractive index layer and the medium refractive index layer contain metal oxide particles such as zirconia particles and titania particles having a higher refractive index than silica particles so as to exhibit a predetermined refractive index. Therefore, in these conventional products, when an antireflection glass having an antireflection film laminated thereon is heated and subjected to bending before glass reinforcement, there is a problem that the antireflection film is cracked and defective products are produced.
As a result of intensive analysis of the occurrence of cracks during bending, the inventors have found that the occurrence of cracks tends to occur mainly in a high refractive index layer containing a large amount of metal oxide particles, and have found that the use of a metal alkoxide oligomer in place of the metal oxide particles can prevent the occurrence of cracks while maintaining a high refractive index, and have thus devised the present invention.
Solution for solving the problem
Namely, the present invention is an antireflection glass characterized in that,
which is an antireflection glass comprising a glass substrate, an antireflection film and a protective layer in this order,
the antireflection film includes, in order from the glass substrate side:
a medium refractive index layer having a refractive index of 1.67 to 1.87 and a film thickness of 35 to 120 nm;
A high refractive index layer having a refractive index of 1.90 to 2.05 and a film thickness of 30 to 115 nm; and
a low refractive index layer having a refractive index of 1.34 to 1.45 and a film thickness of 45 to 120nm,
the protective layer has a refractive index of 1.42 to 1.48 and a film thickness of 5 to 50nm, the high refractive index layer is formed from a cured product of a curable composition containing a metal alkoxide oligomer (the metal is a titanium atom or a zirconium atom), the average light reflectance of both surfaces of the antireflection glass is 0.6% or less, and the protective layer and each layer of the antireflection film do not crack in bending in which the elongation of the glass surface is 5% or less.
In the above scheme of the anti-reflection glass, it is desirable that:
1) The medium refractive index layer is formed from a cured product of a curable composition containing 25 to 70 parts by mass of metal oxide particles per 100 parts by mass of a binder component formed from an alkoxysilane compound represented by the following formula (1) or a partial hydrolysate thereof,
R n -Si(OR 1 ) 4-n (1)
(wherein R is an alkyl group, an alkenyl group or an alkoxyalkyl group, R 1 Is an alkyl group, an alkoxyalkyl group or a halogen atom, and n is an integer of 0, 1 or 2. ) The method comprises the steps of carrying out a first treatment on the surface of the
2) The low refractive index layer is formed from a cured product of a curable composition containing 1 to 15 parts by mass of hollow silica particles and 1 to 10 parts by mass of an aluminum salt hydrate, relative to 100 parts by mass of a binder component formed from an alkoxysilane compound represented by the formula (1) or a partial hydrolysate thereof;
3) The protective layer is formed from a cured product of a curable composition containing 1 to 25 parts by mass of a metal chelate compound and 1 to 20 parts by mass of an aluminum salt hydrate, relative to 100 parts by mass of a binder component formed from an alkoxysilane compound represented by the formula (1) or a partial hydrolysate thereof;
4) In the accelerated weathering test at a temperature of 63℃and a humidity of 50% RH for a test time of 2000 hours, there was no peeling of the antireflection film and the protective layer;
5) Is an anti-reflection glass for chemical strengthening.
The present invention also relates to a method for producing an antireflection reinforced glass, characterized in that the antireflection glass is heated and subjected to bending, and then subjected to chemical reinforcing treatment in a metal salt solution for ion exchange.
ADVANTAGEOUS EFFECTS OF INVENTION
The anti-reflection glass provided by the invention can be subjected to bending processing and is suitable for manufacturing the anti-reflection reinforced glass with high anti-reflection capability.
Such an antireflection reinforced glass product is suitable for use in a large-sized and high-quality, weight-sensitive integrated automobile instrument panel, in addition to a thin glass substrate product, for example, a front protective panel for a capacitive touch panel, a display for various mobile devices such as a digital camera and a cellular phone.
In addition, since the weather resistance is excellent in addition to the bending property, the present invention can be applied to outdoor products having a curved surface such as a spherical monitoring camera cover. Furthermore, the method has the following advantages: even when the antireflection glass is alkali-washed, deterioration of the antireflection film is less likely to occur, and alkali resistance is excellent.
Detailed Description
< anti-reflection glass >
The antireflection glass of the present invention is composed of a glass substrate, an antireflection film, and a protective layer in this order.
The antireflection film is configured in the following order from the glass substrate side:
a medium refractive index layer having a refractive index of 1.67 to 1.87 and a film thickness of 35 to 120 nm;
a high refractive index layer having a refractive index of 1.90 to 2.05 and a film thickness of 30 to 115 nm; and
a low refractive index layer having a refractive index of 1.34 to 1.45 and a film thickness of 45 to 120 nm.
The refractive index of the protective layer is 1.42-1.48, and the film thickness is 5-50 nm.
The anti-reflection glass has optical characteristics that the average light reflectance of both sides is 0.6% or less.
Further, the antireflection glass is characterized in that no crack is generated in each layer of the protective layer and the antireflection film during bending in which the elongation of the glass surface is 5% or less.
The bending test is a test method in which a glass test piece is mounted on a bending die and the test piece is heated by an electric furnace to perform 1 cycle of preheating, bending and heating, and slow cooling, and both of the self-weight bending and the thermal bending by pressing are included. Bending in which the elongation of the glass surface is 5% or less means thermal bending in which the elongation of the glass outermost surface by the test method is 5% or less.
The absence of cracking means that no pattern such as cracking is generated in the perpendicular direction with respect to the elongation direction by surface observation of the curved portion with a laser microscope. The antireflection glass of the present invention is excellent in weather resistance, and is free from peeling between the glass substrate and the antireflection film, interlayer peeling between the refractive index layers, and peeling between the antireflection film and the protective layer.
The present invention is most characterized in that the high refractive index layer uses a metal alkoxide oligomer (the metal is a titanium atom or a zirconium atom) as a refractive index adjuster, and exhibits the above-described bending characteristics. It is presumed that, in the case of using metal oxide particles in the past, interfacial peeling and cracking tend to occur on the surface of the particles when bending treatment is performed, and this can be prevented by using a metal alkoxide oligomer. Furthermore, it is considered that since the hollow silica particle content in the low refractive index layer is reduced, the generation of cracks from the particle surface is also reduced as well.
The antireflection glass of the present invention is further excellent in weather resistance in addition to the optical characteristics and bending characteristics, and peeling between the glass substrate and the antireflection film, interlayer peeling between the refractive index layers, and peeling between the antireflection film and the protective layer are not confirmed. Specifically, in the accelerated weather resistance test at a temperature of 63 ℃ and a humidity of 50% rh (relative humidity) for a test time of 2000 hours, peeling of the antireflection film and the protective layer was not confirmed.
The improvement in the weather resistance is presumed to be due to: the refractive index in the low refractive index layer is set higher, and thus the hollow silica particle content contained in the layer is reduced. Since hollow silica has a cavity inside, ultraviolet rays pass through the cavity to cause deterioration of the layers of the antireflection film. The reduction in the content of the hollow silica particles reduces the amount of ultraviolet rays transmitted through the cavity, and the binder component increases according to the reduced amount, so that the crosslinking density of the layer increases and ultraviolet rays are more difficult to transmit. Further, as described above, since the high refractive index layer does not use metal oxide particles, it is considered that ultraviolet rays are prevented from passing through gaps between particles, and the weather resistance is further improved.
< glass substrate >
The glass substrate is not particularly limited as long as it has a composition that can be strengthened by chemical treatment, and is preferably a glass containing alkali metal ions and alkaline earth metal ions having smaller ionic radii.
Specifically, there may be mentioned: among these, soda lime glass, alkali silicate glass, alkali aluminosilicate glass, aluminoborosilicate glass, borosilicate glass, and the like are preferable, and glass containing sodium ions is most preferable, and glass containing sodium ions in an amount of 5% by weight or more is most preferable.
Alkali aluminosilicate glass is preferably used in view of the fact that a deeper reinforcing layer and high transparency can be obtained by increasing the substitution amount of potassium ions.
The thickness of the glass substrate is usually 2mm to 8mm. If the thickness is less than 2mm, the strength as a tempered glass may be insufficient, and the chemical tempering by the ion exchange method may not be suitable. The area of the substrate is not particularly limited, and may be arbitrarily determined depending on the size of the final product and the restrictions on the manufacturing process.
< antireflection film >
In general, an antireflection film is laminated on the glass substrate, and an antistatic layer, a silica particle layer, an undercoat layer, or a smoke layer (smoke layer) may be provided between the glass substrate and the antireflection film in order to improve the antiglare property and the adhesion, and to prevent the transmission of visible light, within a range where bending characteristics are not deteriorated.
The antireflection film of the present invention is a multilayer antireflection film composed of three refractive index layers having the following characteristics.
Medium refractive index layer: refractive index of 1.67-1.87 and film thickness of 35-120 nm
High refractive index layer: refractive index of 1.90-2.05 and film thickness of 30-115 nm
Low refractive index layer: refractive index of 1.34-1.45 and film thickness of 45-120 nm
The three refractive index layers are arranged in order of the medium refractive index layer, the high refractive index layer, and the low refractive index layer from the glass substrate side.
By adopting the three-layer antireflection film, the average light reflectance of the antireflection glass and the antireflection reinforced glass on both sides at the wavelength of 380-780 nm is below 0.6%, and the average light transmittance at the wavelength of 380-780 nm is above 99%, so that an antireflection product with high performance can be obtained.
< medium refractive index layer >
Is a refractive index layer located at the lowest layer (glass substrate side) of the antireflection film. Typically laminated on a glass substrate.
The refractive index of the medium refractive index layer is 1.67-1.87, and the layer thickness is 35-120 nm. Preferably, the refractive index is 1.70 to 1.76 and the layer thickness is 80 to 100nm.
Since the intermediate refractive index layer needs to be glass reinforced by chemical treatment after the formation of the antireflection film and the protective layer, it is preferable to prepare a curable composition for forming an intermediate refractive index layer (intermediate refractive index layer forming solution) containing the following components, coat the solution, dry, and heat the solution to form the intermediate refractive index layer.
Specifically, the curable composition comprises: the adhesive composition comprises 25 to 70 parts by mass of metal oxide particles per 100 parts by mass of an adhesive component comprising an alkoxysilane compound represented by the following formula (1) or a partial hydrolysate thereof (hereinafter also referred to as alkoxysilane compound or the like).
R n -Si(OR 1 ) 4-n (1)
(wherein R is an alkyl group, an alkenyl group or an alkoxyalkyl group, R 1 Is an alkyl group, an alkoxyalkyl group or a halogen atom, and n is an integer of 0, 1 or 2. )
[ alkoxysilane Compound or partial hydrolysate thereof ]
Is a component that functions as a binder for forming a dense high-strength layer having good adhesion to a glass substrate, and is represented by the above formula (1).
Wherein R is an alkyl, alkenyl or alkoxyalkyl group.
The number of carbon atoms of the alkyl group is preferably 1 to 9, more preferably 1 to 5. Examples of the alkyl group include: methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like.
The number of carbon atoms of the alkenyl group is preferably 1 to 9, more preferably 1 to 5. Examples of the alkenyl group include: ethenyl, propenyl, butenyl, pentenyl, hexenyl, and the like.
The number of carbon atoms of the alkoxyalkyl group is preferably 1 to 9, more preferably 1 to 5. The alkoxy group of the alkoxyalkyl group includes: methoxy, ethoxy, propoxy, and the like. Examples of the alkyl group of the alkoxyalkyl group include: methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like.
Wherein R is 1 Is an alkyl group, an alkoxyalkyl group, or a halogen atom.
Alkyl and alkoxyalkyl are each the same as R.
Examples of the halogen atom include: fluorine, chlorine, bromine, iodine, and the like.
Specific alkoxysilane compounds and the like are: methyltrimethoxysilane, methyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-butoxysilane, vinyltriethoxysilane, and the like.
[ Metal oxide particles ]
The medium refractive index layer is mixed with metal oxide particles in order to control the predetermined refractive index.
As the metal oxide particles, a substance having a refractive index of 1.50 or more can be used. For example, at least one oxide particle selected from the group consisting of titanium oxide, zirconium oxide, niobium pentoxide, antimony doped tin oxide (ATO), indium oxide-tin oxide (ITO), phosphorus doped tin oxide (PTO), fluorine doped tin oxide (FTO), and antimony pentoxide is preferable.
More specifically, as the metal oxide particles, titanium oxide particles (refractive index=2.71), composite titanium metal oxide particles in which titanium oxide is composited with other oxides such as silicon oxide and zirconium oxide at a molecular level to adjust the refractive index, or the like are used. These metal oxide particles are appropriately combined to adjust to a desired refractive index. Such particles are known per se and are commercially available.
The average particle diameter of the metal oxide particles is preferably 1 to 100nm, more preferably 1 to 70nm. The refractive index of the metal oxide particles is preferably 2.00 to 2.90, more preferably 2.10 to 2.80. In the present invention, the average particle diameter means: particle diameter at 50% by volume is accumulated in particle size distribution measured by a laser diffraction-scattering method.
The content of the metal oxide particles in the medium refractive index layer composition is preferably 25 to 70 parts by mass, and is preferably selected so as to satisfy the predetermined refractive index in consideration of a change in refractive index or the like caused by shrinkage of the alkoxysilane compound or the like due to thermal history in a range of 25 to 50 parts by mass, relative to 100 parts by mass of the alkoxysilane compound or the like. In particular, titanium oxide particles having a high refractive index are preferably used for the purpose of designing the refractive index of the medium refractive index layer to be high and for the purpose of suppressing shrinkage itself of the layer by maintaining a balance with the fluctuation of the refractive index of the high refractive index layer.
[ solution for Forming Medium refractive index layer ]
The above-mentioned components constituting the intermediate refractive index layer and optional components as needed are dissolved in an organic solvent described below for the purpose of viscosity adjustment and coatability, and a curable composition for forming the intermediate refractive index layer (hereinafter also referred to as an intermediate refractive index layer forming solution) is prepared. In this solution, an aqueous acid solution such as an aqueous hydrochloric acid solution may be mixed in an appropriate amount in order to promote hydrolysis and condensation of the alkoxysilane compound.
As typical organic solvents, alcohol solvents such as methanol, ethanol, isopropanol, ethylcellosolve, and ethylene glycol; ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as acetone and methyl ethyl ketone; aromatic solvents such as toluene and xylene. Particularly preferably, an alcohol solvent is used.
When a commercially available metal oxide particle dispersion is used, the dispersion medium is inevitably mixed into the medium refractive index layer forming solution. The dispersion medium in the solution and the organic solvent to be mixed separately are removed in the subsequent drying and thermosetting steps.
The amount of the organic solvent used may be in a range suitable for coating, such as a range in which the viscosity of the solution for forming does not drop. In general, the organic solvent may be used in an amount of 0.1 to 20% by weight based on the total weight of the total solid content concentration. The amount of the organic solvent is a value including the amount of the dispersion medium containing the metal oxide particle dispersion.
[ formation of intermediate refractive index layer ]
The medium refractive index layer forming solution is applied to the glass substrate, dried, and then heated to be cured to form the medium refractive index layer. However, from the viewpoints of productivity and adhesion of the layers of the antireflection film, the heat curing step by heating is preferably performed at once after the high refractive index layer and the low refractive index layer, which will be described later, are coated in the same manner until they are dried. Further, it is particularly preferable that all layers of the antireflection film and the protective layer are heat-cured at once after the same coating and drying as before the protective layer.
The coating method is not particularly limited, and dip coating, roll coating, die coating, flow coating, spray coating, and the like can be used, and dip coating is preferable from the viewpoints of appearance quality and layer thickness control.
Drying is usually carried out in the atmosphere at a temperature of 70 to 100℃for 0.25 to 1 hour. The heating for thermal curing is usually carried out in the atmosphere at 300 to 500 ℃ for 0.5 to 2 hours.
< high refractive index layer >
The refractive index layer is laminated on the intermediate refractive index layer (on the viewing side), and has a refractive index higher than that of the intermediate refractive index layer.
The high refractive index layer has a refractive index of 1.90-2.05 and a layer thickness of 30-115 nm. Preferably, the refractive index is 1.95-2.03 and the layer thickness is 45-100 nm.
The invention has the following characteristics: in order to exhibit a high refractive index and not crack the layers during the bending process, a metal alkoxide oligomer is used instead of the conventional metal oxide particles. In the case of using the metal alkoxide oligomer, the following characteristics are also provided: exhibits a higher high refractive index and a long pot life of the high refractive index layer forming solution.
The metal alkoxide oligomer means: zirconium alkoxide compounds or titanium alkoxide compounds are condensed by partial hydrolysis, and have an oligomer having a titanyl bond in the molecule, for example. The production method of the oligomer is described in detail in Japanese patent application laid-open No. 2015-3896, and is typically carried out by hydrolyzing titanium alkoxide such as titanium tetrabutoxide in the presence of pyrazolone hydrochloride. The oligomer is commercially available.
Since the high refractive index layer is not mixed with the refractive index adjusting oxide particles, ultraviolet rays that pass through the gaps between the particles can be prevented, and weather resistance can be improved.
[ solution for Forming high refractive index layer ]
The curable composition (high refractive index layer forming solution) for forming the high refractive index layer is prepared by dissolving the metal alkoxide oligomer as a main component of the high refractive index layer and, if necessary, any components such as metal oxide particles and metal chelate compound in the organic solvent.
The amount of the organic solvent used may be in a range suitable for coating, such as a range in which the viscosity of the solution for forming does not drop. In general, the organic solvent may be used in an amount of 0.1 to 20% by weight based on the total weight of the metal alkoxide oligomer. In the case of using a commercially available metal alkoxide oligomer, the amount of the organic solvent is a value including the amount of the solvent such as alcohol in which the metal alkoxide oligomer is dissolved.
[ formation of high refractive index layer ]
The high refractive index layer forming solution is applied to the medium refractive index layer, dried, and then heated to be cured to form the high refractive index layer.
Coating methods, drying conditions, heating conditions, and the like are used in accordance with the method for forming the medium refractive index layer. The same applies to the case where all layers are preferably heated at once and thermally cured.
< Low refractive index layer >
The refractive index layer located on the outermost layer (visual field side) of the antireflection film is the layer that contributes most to the antireflection ability.
The low refractive index layer has a refractive index of 1.34-1.45 and a layer thickness of 45-120 nm. Preferably, the refractive index is 1.37 to 1.42 and the layer thickness is 55 to 90nm.
Since glass reinforcement is required to be performed by chemical treatment after formation of the antireflection film and the protective layer, and further, in order to exhibit alkali resistance, it is preferable to prepare a curable composition (low refractive index layer forming solution) for forming the low refractive index layer, which contains the following components, and to coat, dry, and heat the solution.
Specifically, the curable composition comprises: the adhesive composition comprises 1 to 15 parts by mass of hollow silica particles and 1 to 10 parts by mass of aluminum salt hydrate, relative to 100 parts by mass of an adhesive component formed from an alkoxysilane compound represented by the formula (1) or a partial hydrolysate thereof.
[ alkoxysilane Compound or partial hydrolysate thereof ]
The compound represented by the above formula (1) is as described in the medium refractive index layer item. Alkoxysilane compounds and the like for forming the medium refractive index layer can be used similarly for the same purpose.
[ hollow silica particles ]
In the low refractive index layer of the present invention, hollow silica particles are used in order to control the refractive index to 1.34 to 1.45.
The hollow silica particles are particles formed of silica having voids therein, and are usually fine hollow particles having a particle diameter of 5 to 150nm and a shell layer thickness of about 1 to 15 nm. Ion exchange is performed by using the internal cavity. In order to control the refractive index of the low refractive index layer within the above range, it is preferable to select hollow silica particles having a refractive index within a range of 1.20 to 1.38.
The hollow silica particles are known from, for example, japanese patent application laid-open No. 2001-233611, and are generally commercially available in the form of a dispersion of a lower alcohol such as methanol, ethanol, propanol, etc., and therefore are preferably commercially available for use.
The hollow silica particles are preferably used in an amount of 1 to 15 parts by mass based on 100 parts by mass of the alkoxysilane compound or the like, and are appropriately selected from the range of 3 to 10 parts by mass in consideration of the change in refractive index due to thermal history, the refractive index balance with the medium refractive index layer or the high refractive index layer, and the like, so as to satisfy the above-described predetermined refractive index.
In particular, setting the content to the above range low and setting the refractive index to be high improves the weather resistance. This is considered to be because the hollow silica particle content is reduced, so that voids through which ultraviolet rays that deteriorate the respective layers of the antireflection film pass are reduced, and the binder component is increased according to the reduction, so that the crosslinking density of the layers is increased, and ultraviolet rays hardly pass.
[ aluminum salt hydrate ]
In order to impart high alkali resistance to the antireflection glass of the present invention, it is preferable to include an aluminum salt hydrate in the low refractive index layer and the protective layer.
The tempered glass requires an alkali cleaning step for the purpose of preventing the tempered glass from becoming frosted glass and losing transparency after production (preventing burn). Further, alkali cleaning is performed for various purposes such as removal of impurities and the like adhering to the glass during the glass strengthening.
Specific examples of burns include: alkali ion deficiency phenomenon, namely blushing, of the glass surface caused by water erosion in the air; and whitening, which is a phenomenon in which a carbonic acid compound is generated due to drying and concentration of moisture containing alkali ions and carbon dioxide gas on the surface of glass. These burns are phenomena that once generated are difficult to repair without physical surface abrasion.
However, by performing this alkali cleaning, the following problems sometimes occur: the antireflection film formed on the glass surface becomes mottled due to damage, becomes uneven or has a reduced film thickness, and does not exhibit a desired antireflection capability; or the color is changed, and the product value is lost.
Aluminum salt hydrate means: a hydrated compound obtained by adding water molecules to an aluminum salt in the form of crystal water, coordinated water, or the like. In the case of a non-hydrate, aggregation or sedimentation may occur during mixing due to lack of affinity with other components. Particularly, in the case of an anhydrous salt having a hygroscopic property, the salt reacts with moisture in the air when a low refractive index forming solution described later is coated, and it is difficult to form a low refractive index layer uniformly. In addition, other metal salt hydrates do not perform well in alkali resistance.
Aluminum is a metal capable of coordinating the binder component, and aluminum oxide which is not likely to be intruded by alkali is presumably generated in the refractive index layer, and thus alkali resistance is exhibited.
Representative examples of the aluminum salt hydrate include: aluminum chloride trihydrate, aluminum chloride hexahydrate, aluminum bromide hexahydrate, aluminum nitrate nonahydrate, aluminum hydroxide trihydrate, aluminum acetate n-hydrate, aluminum sulfate n-hydrate, and the like, and aluminum chloride trihydrate and aluminum chloride hexahydrate are particularly preferable in terms of alkali resistance and scratch resistance.
When the low refractive index layer contains an aluminum salt hydrate, 1 to 10 parts by mass of the aluminum salt hydrate is used per 100 parts by mass of the alkoxysilane compound or the like. When the amount is less than 1 part by mass, the effect thereof is not exhibited. If it exceeds 10 parts by mass, it is not preferable because it is excessively contained in the alkoxysilane compound or the like, and the intermolecular bond strength of the alkoxysilane compound or the like itself is lowered, resulting in lowering of the layer hardness.
[ solution for Forming Low refractive index layer ]
The above-mentioned components constituting the low refractive index layer and optional components such as an aqueous acid solution as needed are dissolved in the above-mentioned organic solvent to prepare a solution for forming the low refractive index layer.
The amount of the organic solvent used is a value including the amount of the dispersion medium in the case of using a commercially available hollow silica particle dispersion.
[ formation of Low refractive index layer ]
The low refractive index layer forming solution is applied to the high refractive index layer, dried, and then heated to be cured to form the low refractive index layer.
Coating methods, drying conditions, heating conditions, and the like are used in accordance with the method for forming the medium refractive index layer. The same applies to the case where all layers are preferably heated at once and thermally cured.
< protective layer >
On the antireflection film (on the viewing side), a protective layer is provided to prevent damage to the antireflection film due to external impact such as scratch, and further to prevent damage caused by ion collision to the antireflection film during chemical strengthening.
The refractive index of the protective layer is 1.42-1.48, and the film thickness is 5-50 nm. Preferably, the refractive index is 1.42 to 1.46 and the layer thickness is 10 to 30nm.
The protective layer is preferably formed as follows: a curable composition (protective layer forming solution) for forming a protective layer is prepared, and the solution is coated, dried, and heated, wherein the curable composition contains 1 to 25 parts by mass of a metal chelate compound and 1 to 20 parts by mass of an aluminum salt hydrate per 100 parts by mass of a binder component formed from an alkoxysilane compound represented by the formula (1) or a partial hydrolysate thereof.
[ Metal chelate Compound ]
Is a component having a function as a crosslinking agent, and makes the formed layer denser.
The metal chelate compound is a compound in which a chelating agent typified by a bidentate ligand is incorporated in a metal such as titanium, zirconium, or aluminum.
Specifically, there may be mentioned: titanium chelate compounds such as triethoxy-mono (acetylacetonate) titanium, diethoxy-bis (acetylacetonate) titanium, monoethoxy-tris (acetylacetonate) titanium, tetra (acetylacetonate) titanium, triethoxy-mono (ethylacetoacetate) titanium, diethoxy-bis (ethylacetoacetate) titanium, monoethoxy-tris (ethylacetoacetate) titanium, bis (ethylacetoacetate) titanium, tris (ethylacetoacetate) titanium;
Zirconium chelate compounds such as triethoxy-mono (acetylacetonato) zirconium, diethoxy-bis (acetylacetonato) zirconium, monoethoxy-tris (acetylacetonato) zirconium, tetra (acetylacetonato) zirconium, triethoxy-mono (ethylacetoacetate) zirconium, diethoxy-bis (ethylacetoacetate) zirconium, monoethoxy-tris (ethylacetoacetate) zirconium, tetra (ethylacetoacetate) zirconium, tris (ethylacetoacetate) zirconium, bis (ethylacetoacetate) zirconium, tris (ethylacetoacetate) zirconium, and the like;
aluminum chelate compounds such as diethoxy aluminum mono (acetylacetonate), monoethoxy aluminum bis (acetylacetonate), di-isopropoxy aluminum mono (acetylacetonate), monoethoxy aluminum bis (ethylacetoacetate), diethoxy aluminum mono (ethylacetoacetate), and aluminum tris (acetylacetonate);
etc.
The metal chelate compound is used in an amount of 1 to 25 parts by mass, preferably 5 to 20 parts by mass, per 100 parts by mass of the alkoxysilane compound or the like. If it exceeds 25 parts by mass, the metal chelate compound is crystallized in the protective layer, resulting in a decrease in anti-reflection ability and poor appearance. When the amount is less than 1 part by mass, the strength and hardness of the layer tend to be lowered, and the function as a protective layer tends not to be exhibited.
[ aluminum salt hydrate ]
The aluminum salt hydrate used to form the low refractive index layer may be used identically for the same purpose.
The aluminum salt hydrate is used in an amount of 1 to 20 parts by mass, preferably 3 to 15 parts by mass, per 100 parts by mass of the alkoxysilane compound or the like. If it exceeds 20 parts by mass, the layer hardness tends to be lowered. In the case of less than 1 part by mass, it is difficult to exhibit an alkali resistance effect.
[ solution for Forming protective layer ]
The above-mentioned components constituting the protective layer and optional components such as an aqueous acid solution as needed are dissolved in the above-mentioned organic solvent to prepare a solution for forming the protective layer.
[ formation of protective layer ]
The protective layer-forming solution is applied to the low refractive index layer, dried, and then heated to be cured to form a protective layer.
Coating methods, drying conditions, heating conditions, and the like are used in accordance with the method for forming the medium refractive index layer. The same applies to the case where it is preferable to heat and cure all the layers including the antireflection film at one time.
< chemical treatment-based glass tempering >
The anti-reflection glass of the present invention is chemically treated to form a glass-strengthened anti-reflection strengthened glass.
By chemical treatment, metal ions (e.g., sodium ions) having a small ionic radius contained in the glass are replaced with metal ions (e.g., potassium ions) having a larger ionic radius, and strengthening is performed. That is, by substituting a metal ion having a smaller ionic radius with a metal ion having a larger ionic radius, a compressive stress layer is formed on the surface of the glass. As a result, in order to break the glass, a force to remove the compressive stress on the surface is required in addition to the force to break the intermolecular bond, and the strength is significantly improved as compared with the conventional glass.
As the chemical treatment method, a conventionally known method can be used. Typically, a high-strength tempered glass is produced by bringing unreinforced antireflection glass into contact with a molten metal salt of potassium salt such as potassium nitrate at 390 to 450 ℃ for 3 to 16 hours, and substituting sodium ions having a small ionic radius with potassium ions having a large ionic radius.
< alkali cleaning >
In the preceding or subsequent steps of the glass strengthening step, alkali cleaning is performed for the purpose of removing organic/inorganic substances adhering to the glass surface, for the purpose of preventing glass from becoming frosted and vitrified to lose transparency (preventing burn-out), and for other reasons.
In the alkali cleaning, an alkali cleaning liquid having a pH of about 12 to 13, which is obtained by dissolving a strong alkali compound such as sodium hydroxide or potassium hydroxide, a surfactant, or the like in an alcohol-based solvent or water, is commercially available, and therefore, the cleaning liquid is suitably diluted with water or the like depending on the purpose of alkali cleaning or the alkali cleaning conditions.
The alkali washing is usually carried out at room temperature to 55 ℃ for about 0.1 to 0.5 hours, and then the alkali washing liquid is washed away by water and an organic solvent.
Examples (example)
The present invention will be specifically described below by way of examples, but the present invention is not limited to these examples. Furthermore, the combination of the features described in the embodiments is not necessarily all necessary for the solution of the present invention.
The various components and abbreviations used in the examples and comparative examples below, as well as the test methods, are as follows.
[ aluminum salt hydrate ]
AlCl 3 ·6H 2 O: aluminum chloride hexahydrateComposition
[ alkoxysilane Compound etc. ]
TEOS: tetraethoxysilane
[ Metal chelate Compound ]
Aluminum D: monoacetylacetonate bis (ethylacetoacetate) aluminum
[ silica particles ]
Hollow silica particles:
average particle diameter of 40nm, refractive index of 1.25, solid content of 20 wt%,
Dispersion solvent IPA
[ Metal oxide particles ]
Titanium oxide particles:
average particle diameter of 108.8nm, refractive index of 2.71, solid content of 15 wt%,
Methanol as a dispersing solvent
[ Metal alkoxide oligomer ]
Ti oligomer: oligomers prepared from titanium tetra (n-butoxy) as main raw material
Solvent n-butanol
[ organic solvent ]
IPA: isopropyl alcohol
BuOH: n-butanol
Eta coool: ethanol/isopropanol mixture
NPA: n-propanol
SBAC: acetic acid sec-butyl ester
[ hydrolysis catalyst ]
HCl:0.05N hydrochloric acid
[ others ]
TTB: titanium tetrabutoxide (IV)
[ glass substrate ]
Glass 1.1: soda ash glass (soda ash glass,50 mm. Times.88 mm. Times.1.1 mm)
[ refractive index of refractive index layers ]
The solution for forming each refractive index layer was applied to a glass substrate at a thickness of 100nm, and cured to form each refractive index layer or protective layer. The reflectance of each layer was measured by using a "spectrophotometer V-650" manufactured by Nippon Spectrophotometer Co., ltd, and the refractive index was calculated.
[ average light reflectance of both sides ]
The average light reflectance (hereinafter also referred to as average light reflectance) of both surfaces was measured as follows.
The measurement was performed at 380nm to 780nm using an "ultraviolet-visible spectrophotometer V-650" manufactured by Nippon Spectrophotometer Co., ltd, and the weight coefficient was multiplied by JIS Z8722 to calculate the measurement. The object to be measured is an antireflection glass having an antireflection film and a protective layer formed on both surfaces of a glass substrate. The measured values were values of the antireflection glass before glass strengthening, but it was confirmed that the values were hardly changed after glass strengthening.
[ average light transmittance ]
The average light transmittance was measured as follows. The measurement was performed at 380nm to 780nm using an "ultraviolet-visible spectrophotometer V-650" manufactured by Nippon Spectrophotometer Co., ltd, and the weight coefficient was multiplied by JIS Z8722 to calculate the measurement. The measured values were values of the antireflection glass before glass strengthening, but it was confirmed that the values were hardly changed after glass strengthening.
[ bending Property ]
The bending test refers to: the test method in which the glass test piece is mounted on the bending die and the test piece is heated by an electric furnace to perform 1 cycle of preheating, bending and heating, and slow cooling, is one of the self-weight bending and the thermal bending by pressing. The test was conducted using soda lime glass, and preheating, molding and heating were conducted at 600.+ -. 10 ℃ for 10 to 30 minutes, and the glass was subjected to gravity bending until the elongation of the glass surface was 5%.
The elongation was measured and calculated as follows. The arc width (w) and the arc height (h) of the outermost surface of the bent glass were measured, and the R value of the outermost surface of the glass was calculated according to the following known formula.
Next, using the obtained R value, the thickness (t) of the glass, θ=90° (right angle bending condition), elongation was determined according to the following formula.
The surface observation was performed on the part after bending by a laser microscope, and no streak (crack) cracking in the perpendicular direction to the elongation direction was used as an evaluation criterion.
O: no crack
X: crack generation
Weather resistance: accelerated weathering test ]
The weather resistance test was performed by the solar carbon arc lamp type weather resistance test at BP63℃and humidity 50% RH (relative humidity) for a test time of 2000 hours. The measuring apparatus, conditions and method are based on JIS B7753. The dicing tape test was performed, and the evaluation was performed with the anti-reflective coating and the protective layer not peeled off as a standard.
O: film-free peeling
X: film peeling
[ alkali resistance of antireflection film ]
To examine alkali resistance of the antireflection film by alkali cleaning, alkali cleaning was performed in the following manner, and changes in the color of the antireflection reinforced glass before alkali cleaning and after alkali cleaning were observed with naked eyes, and evaluation was performed according to the following criteria.
For the obtained antireflective glass, "SEMICLEAN MG" manufactured by yokohama oil industry Co., ltd; ph=12.4″ in a diluted solution diluted with water by 5wt%, alkaline washing was performed by immersing at 40 ℃ for 10 minutes under ultrasonic waves, and then washing the washing solution with warm water and IPA. Then, the glass was immersed in a molten potassium nitrate solution at 390℃for 16 hours to perform a chemical strengthening treatment, thereby obtaining an antireflection strengthened glass.
The anti-reflection glass (not strengthened) is colorless and transparent in color. The reinforced antireflection reinforced glass was evaluated.
In the case of "very" and "good", it means that the antireflection film is optically not deteriorated by alkali cleaning. "X" indicates that peeling of the antireflection film clearly occurred.
And (3) the following materials: no change
O: can see the change of color tone but no peeling
X: film peeling
[ glass strength; compression stress value measurement ]
The surface stress CS (MPa) and the depth of stress layer DOL (μm) due to the refractive index difference (due to ion substitution) of the chemically strengthened glass surface were measured using "FSM-6000LE" manufactured by the Producer Corp. The larger the CS and DOL values, the greater the degree of reinforcement. If the DOL value is 10 μm or more, it is sufficient to function as a tempered glass.
[ preparation of solution for Forming Medium refractive index layer ]
The components shown in Table 1 were mixed in the amounts shown in the tables to prepare medium refractive index layer forming solutions (m-1 to m-5).
TABLE 1
Solution for forming medium refractive index layer
[ preparation of solution for Forming high refractive index layer ]
The components shown in Table 2 were mixed in the amounts shown in the tables to prepare solutions (h-1 to h-3) for forming a high refractive index layer.
h-2 is a solution of a tetraalkoxy metal compounded in place of the metal alkoxide oligomer. h-3 is a solution compounded with metal oxide particles.
TABLE 2
Solution for forming high refractive index layer
[ preparation of solution for Forming Low refractive index layer ]
The components shown in Table 3 were mixed in the amounts shown in the tables to prepare solutions (l-1 to l-9) for forming a low refractive index layer.
l-9 is a solution free of aluminum salt hydrate.
TABLE 3
[ preparation of solution for Forming protective layer ]
The components shown in Table 4 were mixed in the amounts shown in the tables to prepare solutions (cv-1 to cv-8) for forming a protective layer.
cv-7 is a solution containing no aluminum salt hydrate, and cv-8 is a solution containing an excessive amount of aluminum salt hydrate.
TABLE 4
/>
Example 1
After immersing glass 1.1 (glass substrate) in the medium refractive index layer forming solution (m-2), the glass substrate was dried at 100℃for 15 minutes to form an uncured medium refractive index layer having a layer thickness of 86nm on the glass substrate. It is considered that the intermediate refractive index layer is not sufficiently cured by the drying under the above conditions, and the following layers are also formed. The layer thickness was adjusted by the lifting speed from the immersed medium refractive index layer forming solution. The following layers are also similar.
Then, the glass substrate was immersed in the high refractive index layer forming solution (h-1), and then dried at 100℃for 15 minutes, whereby an uncured high refractive index layer having a layer thickness of 51nm was formed on the uncured medium refractive index layer.
Then, the glass substrate was immersed in the low refractive index layer forming solution (l-1), and then dried at 100℃for 15 minutes, whereby an uncured low refractive index layer having a layer thickness of 88nm was formed on the uncured high refractive index layer.
Then, the glass substrate was immersed in a protective layer forming solution (cv-1), and then dried at 100℃for 15 minutes, to form an uncured protective layer having a layer thickness of 10nm on the uncured low refractive index layer.
The anti-reflection glass of the present invention was produced by thermally curing a glass substrate obtained by laminating the above-mentioned uncured anti-reflection film and the protective layer at 300 ℃ for 30 minutes.
The average light reflectance and average light transmittance of the obtained antireflective glass were measured by the above-mentioned methods, and are shown in table 5 together with the layer thicknesses and refractive indices of the respective layers.
Further, the alkali cleaning and glass strengthening of the antireflection glass were performed as follows. For the above-mentioned antireflection glass, "SEMICLEAN MG" manufactured by yokohami oil industry Co., ltd; ph=12.4″ in a dilution of 5wt% with water, alkali washing was performed by immersing at 40 ℃ for 10 minutes under ultrasonic waves, and then washing the washing liquid with warm water and IPA. Next, the glass was immersed in a molten potassium nitrate solution at 390℃for 16 hours to perform chemical strengthening treatment, thereby obtaining an antireflection strengthened glass.
The bending properties, weather resistance, glass strength and alkali resistance of the obtained antireflection reinforced glass were measured by the methods described above. The results are shown in Table 5.
Examples 2 to 16
An antireflection glass and an antireflection reinforced glass were produced in the same manner as in example 1, except that the refractive index layer forming solution and the protective layer forming solution were used in combination as shown in tables 5 and 6.
Tables 5 and 6 show the average light reflectance and average light transmittance of the obtained antireflection glass, the layer thicknesses of the respective layers, the refractive index, and the bending characteristics, weather resistance, glass strength, and alkali resistance of the antireflection reinforced glass.
When the high refractive index layer is formed of a cured product of a curable composition containing a metal alkoxide oligomer, the protective layers and the antireflection film do not crack under bending at an elongation of 5%.
TABLE 5
TABLE 6
Comparative examples 1 to 14 and reference examples 1 to 6
An antireflection glass and an antireflection reinforced glass were produced in the same manner as in example 1, except that the refractive index layer forming solution and the protective layer forming solution were used in combination as shown in tables 7 and 8.
Tables 7 and 8 collectively show the average light reflectance and average light transmittance of the obtained antireflection glass, the layer thicknesses and refractive indices of the respective layers, and the bending properties, weather resistance, glass strength, and alkali resistance of the antireflection reinforced glass.
TABLE 7
TABLE 8
Note that "-" indicates that the layer was not normally formed, and that the optical characteristics were not measured
Comparative example 1 shows a case where the refractive index of the low refractive index layer is high, and comparative example 2 shows a case where the refractive index of the low refractive index layer is low, and the antireflection capability is poor.
Comparative example 3 shows a case where the refractive index of the medium refractive index layer is low, and comparative example 4 shows a case where the refractive index of the medium refractive index layer is high, and the antireflection capability is poor.
Comparative example 5 was a case where the layer thickness of the low refractive index layer was thin, and comparative example 6 was a case where the layer thickness of the low refractive index layer was thick, and the antireflection capability was poor.
In comparative example 7, the thickness of the high refractive index layer was small, and in comparative example 8, the thickness of the high refractive index layer was large, and the antireflection performance was insufficient.
In comparative example 9, the intermediate refractive index layer was thin, and in comparative example 10, the intermediate refractive index layer was thick, and the antireflection performance was insufficient.
Comparative example 11 is a case where a silane coupling agent and titanium oxide particles are used in place of the metal alkoxide oligomer in the high refractive index layer, and the antireflection capability is insufficient.
In comparative example 12, in the case of using a tetraalkoxy metal in place of the metal alkoxide oligomer in the high refractive index layer, the solution was cured quickly, the layer thickness was uneven, and the refractive index was uneven during the heat curing, which was not controllable. Therefore, the antireflection capability and other characteristics could not be measured.
Comparative example 13 is a case where the protective layer is thin, alkali resistance is poor, and comparative example 14 is a case where the protective layer is thick, average light reflectance is poor.
Reference example 1 is a case where a metal chelate compound is not used in the protective layer, and alkali resistance is poor.
Reference example 2 is a case where the metal chelate compound is excessively used in the protective layer, and the bending property is poor.
Reference example 3 shows that alkali resistance is poor when an aluminum salt hydrate is not used in the protective layer.
Reference example 4 is a case where an aluminum salt hydrate is excessively used in the protective layer, the protective layer whitens, and the anti-reflection ability is not exhibited.
Reference example 5 is a case where an aluminum salt hydrate was excessively used in the low refractive index layer, and the low refractive index layer was whitened and did not exhibit anti-reflection ability.
Reference example 6 shows that the low refractive index layer does not use an aluminum salt hydrate, and exhibits sufficient reflection characteristics and bending characteristics, but is poor in alkali resistance.
Claims (7)
1. An anti-reflection glass, which is characterized in that,
which is an antireflection glass comprising a glass substrate, an antireflection film and a protective layer in this order,
the antireflection film includes, in order from the glass substrate side:
a medium refractive index layer having a refractive index of 1.67 to 1.87 and a film thickness of 35 to 120 nm;
A high refractive index layer having a refractive index of 1.90 to 2.05 and a film thickness of 30 to 115 nm; and
a low refractive index layer having a refractive index of 1.34 to 1.45 and a film thickness of 45 to 120nm,
the refractive index of the protective layer is 1.42-1.48, the film thickness is 5-50 nm,
the high refractive index layer is formed from a cured product of a curable composition containing a metal alkoxide oligomer, wherein the metal is a titanium atom or a zirconium atom,
the average light reflectance of both surfaces of the antireflection glass is 0.6% or less, and no crack is generated in each of the protective layer and the antireflection film in bending in which the elongation of the glass surface is 5% or less.
2. The antireflection glass according to claim 1, wherein the medium refractive index layer is formed of a cured product of a curable composition containing 25 to 70 parts by mass of metal oxide particles per 100 parts by mass of a binder component formed of an alkoxysilane compound represented by the following formula (1) or a partial hydrolysate thereof,
R n -Si(OR 1 ) 4-n (1)
wherein R is an alkyl, alkenyl or alkoxyalkyl group, R 1 Is an alkyl group, an alkoxyalkyl group or a halogen atom, and n is an integer of 0, 1 or 2.
3. The antireflection glass according to claim 1, wherein the low refractive index layer is formed of a cured product of a curable composition containing 1 to 15 parts by mass of hollow silica particles and 1 to 10 parts by mass of an aluminum salt hydrate per 100 parts by mass of a binder component formed of an alkoxysilane compound represented by the following formula (1) or a partial hydrolysate thereof,
R n -Si(OR 1 ) 4-n (1)
Wherein R is an alkyl, alkenyl or alkoxyalkyl group, R 1 Is an alkyl group, an alkoxyalkyl group or a halogen atom, and n is an integer of 0, 1 or 2.
4. The antireflection glass according to claim 1, wherein the protective layer is formed of a cured product of a curable composition containing 1 to 25 parts by mass of a metal chelate compound and 1 to 20 parts by mass of an aluminum salt hydrate per 100 parts by mass of a binder component formed of an alkoxysilane compound represented by the following formula (1) or a partial hydrolysate thereof,
R n -Si(OR 1 ) 4-n (1)
wherein R is an alkyl, alkenyl or alkoxyalkyl group, R 1 Is an alkyl group, an alkoxyalkyl group or a halogen atom, and n is an integer of 0, 1 or 2.
5. The antireflection glass according to any one of claims 1 to 4, wherein the antireflection film and the protective layer are not peeled off in an accelerated weathering test at a temperature of 63 ℃ and a humidity of 50% rh for a test time of 2000 hours, and the humidity is a relative humidity.
6. The antireflection glass according to any one of claims 1 to 4, wherein the antireflection glass is an antireflection glass for chemical strengthening.
7. A method for producing an antireflection reinforced glass, comprising heating the antireflection glass according to any one of claims 1 to 4, bending the antireflection glass, and then subjecting the glass to a chemical reinforcing treatment in a metal salt solution for ion exchange.
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