CN111025434A - Anti-reflection glass - Google Patents

Anti-reflection glass Download PDF

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Publication number
CN111025434A
CN111025434A CN201910952566.7A CN201910952566A CN111025434A CN 111025434 A CN111025434 A CN 111025434A CN 201910952566 A CN201910952566 A CN 201910952566A CN 111025434 A CN111025434 A CN 111025434A
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CN
China
Prior art keywords
layer
antireflection
glass
glass substrate
refractive index
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CN201910952566.7A
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Chinese (zh)
Inventor
西森才将
梨木智刚
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Nitto Denko Corp
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Nitto Denko Corp
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Publication of CN111025434A publication Critical patent/CN111025434A/en
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • 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
    • B32B17/061—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 metal
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • 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
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/416—Reflective
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive
    • 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

Abstract

Provided is an antireflection glass having excellent scratch resistance. An antireflection glass (1) is provided with: the antireflection film comprises a glass substrate (2) and an antireflection layer (3) disposed on the upper side of the glass substrate (2), wherein the surface roughness Ra of the upper surface of the antireflection glass (1) is less than 2.0 nm.

Description

Anti-reflection glass
Technical Field
The present invention relates to an antireflection glass, and more particularly to an antireflection glass suitable for optical use.
Background
Conventionally, in an image display device such as a liquid crystal display, an antireflection film is disposed on the outermost surface of a display screen in order to prevent reflection of external light. In the antireflection film, an antireflection layer including a high refractive index layer and a low refractive index layer is generally formed on a resin film.
The antireflection film is disposed on the outermost layer of the screen, and therefore is required to have scratch resistance. Specifically, the antireflection layer must not be peeled off from the resin film by an external impact.
As such an antireflection film, for example, an antireflection film including a resin film, an adhesion layer, and an antireflection layer in this order is disclosed (see patent document 1).
The antireflection film suppresses peeling of the antireflection layer by the adhesion layer.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2014-167621
Disclosure of Invention
Problems to be solved by the invention
In the antireflection film of patent document 1, although peeling of the antireflection layer can be suppressed, a defect that the adhesion layer and the resin film are damaged may occur.
Therefore, in addition to providing the adhesion layer, it has been studied to provide a hard coat layer on the surface of the resin film. However, even when the hard coat layer is provided, there is a problem that damage occurs in each layer such as the hard coat layer, which is not sufficient. Therefore, further improvement in scratch resistance is required.
The invention provides an anti-reflection glass with excellent scratch resistance.
Means for solving the problems
The present invention [1] comprises an antireflection glass comprising: and an antireflection layer disposed on one side of the glass substrate in a thickness direction, wherein a surface roughness Ra of a surface of the antireflection glass on the one side in the thickness direction is less than 2.0 nm.
The invention [2] is the antireflection glass according to [1], wherein the glass substrate has a thickness of 150 μm or less.
The invention [3] comprises the antireflection glass according to [1] or [2], further comprising an antifouling layer disposed on one side in the thickness direction of the antireflection layer.
ADVANTAGEOUS EFFECTS OF INVENTION
The antireflection glass of the present invention comprises a glass substrate and an antireflection layer, and has excellent scratch resistance because the surface roughness Ra of one surface in the thickness direction is less than 2.0 nm.
Drawings
FIG. 1 is a sectional view of an embodiment of an antireflection glass of the present invention.
Fig. 2 shows a modification of the antireflection glass shown in fig. 1 (a form without an antifouling layer).
Description of the reference numerals
1 anti-reflection glass
2 glass substrate
3 anti-reflection layer
4 antifouling layer
Detailed Description
1. Anti-reflection glass
An antireflection glass 1 as an embodiment of the antireflection glass of the present invention will be described with reference to fig. 1.
In fig. 1, the vertical direction on the paper surface is the vertical direction (thickness direction, 1 st direction), the upper side on the paper surface is the upper side (thickness direction side, 1 st direction side), and the lower side on the paper surface is the lower side (thickness direction side, 1 st direction side). The horizontal direction and the depth direction of the paper surface are the plane directions orthogonal to the vertical direction. Specifically, directional arrows in the drawings are used as references.
As shown in fig. 1, the antireflection glass 1 has a thin film shape (including a sheet shape) having a predetermined thickness, and has a flat upper surface (one surface in the thickness direction) and a flat lower surface (the other surface in the thickness direction) extending in a predetermined direction (the surface direction) orthogonal to the thickness direction.
Specifically, the antireflection glass 1 includes: a glass substrate 2, an antireflection layer 3 disposed on the upper side (one side in the thickness direction) of the glass substrate 2, and an antifouling layer 4 disposed on the upper side of the antireflection layer 3. That is, the antireflection glass 1 includes a glass substrate 2, an antireflection layer 3, and an antifouling layer 4 in this order in the vertical direction (thickness direction). The antireflection glass 1 is preferably formed of a glass substrate 2, an antireflection layer 3, and an antifouling layer 4. Each layer will be described in detail below.
(glass substrate)
The glass substrate 2 is the lowermost layer of the antireflection glass 1, and is a support material for supporting the antireflection layer 3 and the antifouling layer 4 while ensuring the mechanical strength of the antireflection glass 1.
The glass substrate 2 has a thin film shape (including a sheet shape) and is formed of transparent glass.
Examples of the glass include alkali-free glass, soda-lime glass, borosilicate glass, and aluminosilicate glass.
The total light transmittance (JIS K7375-.
The thickness of the glass substrate 2 is, for example, 150 μm or less, preferably 120 μm or less, and more preferably 100 μm or less. The thickness of the glass substrate 2 is, for example, 10 μm or more, preferably 30 μm or more. When the thickness of the glass substrate 2 is not more than the upper limit, the flexibility is excellent and the glass substrate can be wound in a roll shape. When the thickness of the glass substrate 2 is not less than the lower limit, the anti-reflection glass 1 is excellent in scratch resistance. Further, the sheet is excellent in mechanical strength and can suppress breakage during roll-to-roll conveyance.
The thickness of the glass substrate 2 can be measured, for example, by using a direct thickness gauge (dial gauge) (manufactured by PEACOCK, "DG-205").
(anti-reflection layer)
The antireflection layer 3 is a layer for preventing reflection of external light such as sunlight and indoor light.
The antireflection layer 3 has a thin film shape. The antireflection layer 3 is disposed on the entire upper surface of the glass substrate 2 so as to be in contact with the upper surface of the glass substrate 2. More specifically, the antireflection layer 3 is disposed between the glass substrate 2 and the antifouling layer 4 so as to be in contact with the upper surface of the glass substrate 2 and the lower surface of the antifouling layer 4. That is, the antireflection layer 3 is in direct contact with the upper surface of the glass substrate 2.
The antireflection layer 3 includes a high refractive index layer 5 and a low refractive index layer 6, and is preferably an alternating stack of the high refractive index layer and the low refractive index layer. Specifically, the antireflection layer 3 is a 4-layer laminate, and includes a 1 st high refractive index layer 5a, a 1 st low refractive index layer 6a, a 2 nd high refractive index layer 5b, and a 2 nd low refractive index layer 6b in this order from below.
The antireflection layer 3 is preferably formed of an inorganic compound such as a metal oxide.
Specifically, the material of the high refractive index layer 5 (1 st high refractive index layer 5a or 2 nd high refractive index layer 5b) may be, for example, niobiumMetal oxides such as oxides, titanium oxides, zirconium oxides, indium tin oxides, and antimony tin composite oxides. Preferably, an oxide of niobium (Nb)2O5)。
The refractive index of the high refractive index layer 5 is, for example, 1.8 or more, and is, for example, 2.4 or less. The refractive index is a refractive index at a wavelength of 550nm, and can be measured, for example, by an Abbe refractometer.
The high refractive index layer 5 has a thickness of, for example, 5nm or more, preferably 10nm or more, for example, 200nm or less, preferably 150nm or less, respectively.
The thickness of the 2 nd high refractive index layer 5b is preferably larger than the thickness of the 1 st high refractive index layer 5a, and the ratio (5b/5a) of the thickness of the 2 nd high refractive index layer 5b to the thickness of the 1 st high refractive index layer 5a is, for example, 2 times or more, preferably 5 times or more, and is, for example, 20 times or less, preferably 15 times or less. When the ratio is in the above range, reflection at the air interface can be further reduced.
Examples of the material of the low refractive index layer 6 (the 1 st low refractive index layer 6a or the 2 nd low refractive index layer 6b) include silicon oxide, magnesium fluoride, and the like. Preferably, silicon oxide (SiO)2)。
The refractive index of the low refractive index layer 6 is, for example, 1.6 or less, and is, for example, 1.3 or more.
The low refractive index layer 6 has a thickness of, for example, 10nm or more, preferably 20nm or more, for example, 200nm or less, preferably 150nm or less, respectively.
The thickness of the 2 nd low refractive index layer 6b is preferably larger than the thickness of the 1 st low refractive index layer 6a, and the ratio (6b/6a) of the thickness of the 2 nd low refractive index layer 6b to the thickness of the 1 st low refractive index layer 6a is, for example, 1.5 times or more, preferably 2 times or more, and, for example, 10 times or less, preferably 5 times or less. When the ratio is in the above range, reflection at the air interface can be further reduced.
The total thickness of the antireflection layer 3 is, for example, 100nm or more, preferably 200nm or more, and is, for example, 1000nm or less, preferably 500nm or less.
The thickness of the anti-reflection layer 3 can be measured, for example, by using a transmission electron microscope (manufactured by Nippon electronics Co., Ltd., "JEM-2100 Plus") or a scanning type fluorescent X-ray analyzer (manufactured by Rigaku Corporation, "ZSX PrimusII").
(antifouling layer)
The stain-proof layer 4 is a layer for preventing contaminants such as fingerprints and dust from adhering to the upper surface of the antireflection glass 1.
The antifouling layer 4 is the uppermost layer of the antireflection glass 1 and has a thin film shape. The stain-proofing layer 4 is disposed on the entire upper surface of the antireflection layer 3 so as to be in contact with the upper surface of the antireflection layer 3.
Examples of the material of the stain-proofing layer 4 include fluorine-based resins such as polytetrafluoroethylene, fluoroethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, polyvinyl fluoride and polyvinylidene fluoride, silicone-based resins such as fluorosilicones, and silane-based compounds such as perfluoropolyether group-containing alkoxysilanes.
The thickness of the antifouling layer 4 is, for example, 0.5nm or more, preferably 1nm or more, and is, for example, 100nm or less, preferably 10nm or less. The thickness of the antifouling layer 4 can be measured, for example, by using a scanning fluorescent X-ray analyzer (manufactured by rigaku corporation, "ZSX Primus II").
The water contact angle of the upper surface of the antifouling layer 4 is, for example, 100 ° or more, preferably 110 ° or more, and is, for example, less than 180 °. When the water contact angle is not less than the lower limit, the antifouling property is excellent. The water contact angle is measured by placing pure water having a diameter of about 2mm on the upper surface of the antifouling layer 4.
The refractive index of the antifouling layer 4 is, for example, 1.35 or more and 1.60 or less. When the refractive index of the stain-proofing layer 4 is in the above range, the difference in refractive index from the antireflection layer 3 (particularly, the 2 nd low refractive index layer 6b) can be reduced, and the antireflection function of the antireflection layer 3 can be more reliably exhibited.
2. Method for producing antireflection glass
Next, a method for producing the antireflection glass 1 will be described. In the production of the antireflection glass 1, for example, in the roll-to-roll process, the antireflection layer 3 and the antifouling layer 4 are provided in this order on the glass substrate 2. Specifically, the long glass substrate 2 is fed from a feed roller in the longitudinal direction and conveyed to the downstream side in the conveying direction, the antireflection layer 3 is provided on the upper surface of the glass substrate 2, the antifouling layer 4 is provided on the upper surface of the antireflection layer 3, and the antireflection glass 1 is wound up by a winding roller. The details will be described below.
First, a long glass substrate 2 wound around a delivery roll is prepared, and the glass substrate 2 is conveyed so as to be wound around a winding roll.
Preferably, the glass substrate 2 having a thickness of 150 μm or less is prepared. This makes it possible to easily wind the sheet around a roll such as a feed roll and a take-up roll.
If necessary, from the viewpoint of adhesion between the glass substrate 2 and the antireflection layer 3, the lower surface or the upper surface of the glass substrate 2 may be subjected to etching treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, or oxidation, or subbing treatment (plasma treatment). The glass substrate 2 may be cleaned and cleaned by solvent cleaning, ultrasonic cleaning, or the like.
Next, the antireflection layer 3 is provided on the upper surface of the glass substrate 2. For example, the antireflection layer 3 is formed on the upper surface of the glass substrate 2 by a dry method.
Examples of the dry method include a vacuum deposition method, a sputtering method, and an ion plating method. A sputtering method is preferably used. That is, the antireflection layer 3 is preferably a sputtered layer formed by sputtering. This improves the adhesion between the glass substrate 2 and the antireflection layer 3, and further improves the abrasion resistance of the antireflection glass 1. In addition, the antireflection layer 3 can be formed into a thin film having a uniform thickness.
In the sputtering method, a target and an adherend (glass substrate 2) are arranged in a vacuum chamber so as to face each other, and gas is supplied and a voltage is applied from a power source, whereby gas ions are accelerated and irradiated onto the target, and a target material is ejected from the target surface, and the target material is laminated on the adherend surface.
Examples of the sputtering method include a 2-pole sputtering method, an electron cyclotron resonance sputtering method, a magnetron sputtering method, an ion beam sputtering method, and the like. A magnetron sputtering method is preferably used.
In the case of the sputtering method, when a reactive gas described later is used in combination as the target material, the simple metal constituting the metal oxide can be mentioned. On the other hand, when the reactive gases are not used in combination, the above-mentioned metal oxides can be cited.
As an example, when the antireflection layer 3 including the 1 st high refractive index layer 5a (e.g., an oxide layer of niobium), the 1 st low refractive index layer 6a (e.g., a silica layer), the 2 nd high refractive index layer 5b (e.g., an oxide layer of niobium), and the 2 nd low refractive index layer 6b (e.g., a silica layer) in this order is formed by using reactive gases in combination, a niobium metal target, a silicon target, a niobium metal target, and a silicon target are disposed in this order in separate film forming chambers in the transport direction, and sputtering is performed.
Examples of the gas used for sputtering (i.e., the gas introduced into the film forming chamber) include inert gases such as argon (Ar). Preferably, reactive gases such as oxygen can be used in combination. Thus, for example, when a metal oxide is formed as the antireflection layer 3, the amount of oxygen can be adjusted, and thus the metal as the target material can be reliably and accurately oxidized. As a result, a metal oxide having a desired function can be formed at a high rate.
When the reactive gases are used in combination, the flow rate (sccm) of the reactive gas is, for example, 0.1% or more, and, for example, 5% or less, based on the total flow rate of the inert gas and the reactive gas.
The gas pressure during sputtering (i.e., the gas pressure in the film forming chamber during film formation) is, for example, less than 1.0Pa, preferably 0.5Pa or less, and, for example, 0.1Pa or more. When the gas pressure is not more than the upper limit, the surface roughness of the obtained antireflection glass 1 can be appropriately adjusted within a desired range (Ra less than 2.0 nm). That is, for example, when sputtering is performed under constant power control at a gas pressure exceeding the upper limit, the amount of the ionized inert gas (for example, Ar ions) and, further, the amount of the ionized inert gas that strikes the target increase, and therefore, the current value increases and the voltage value decreases. Therefore, kinetic energy of the sputtered particles (sputtered target) is reduced, and the antireflection layer 3 laminated on the glass substrate 2 is likely to be a porous film, and as a result, surface roughness is increased. On the other hand, when the gas pressure is not more than the upper limit, the reduction in the voltage value can be suppressed, and the film quality of the antireflection layer 3 to be laminated can be densified. As a result, the upper surface of the antireflection layer 3, and further the upper surface of the antireflection glass 1 can be smoothed.
For the sputtering process, Plasma Emission Monitoring (PEM) control is preferably implemented. Specifically, the plasma emission intensity during discharge is detected, and the amount of gas introduced into the film forming chamber is controlled based on the detection result. This makes it possible to obtain the antireflection layer 3 having a uniform thickness and a desired film quality.
The power source may be any of a DC power source, an AC power source, an MF power source, and an RF power source, for example, or may be a combination thereof.
Next, the antifouling layer 4 is provided on the upper surface of the antireflection layer 3. The antifouling layer 4 is formed on the upper surface of the antireflection layer 3 by, for example, a wet method or a dry method.
In the wet method, for example, a varnish is prepared by diluting the material of the antifouling layer 4 with a solvent, and the varnish is applied to the upper surface of the antireflection layer 3 by various coating methods.
Examples of the coating method include roll coating, doctor blade coating, spin coating, bar coating, die coating, gravure coating, reverse coating, and screen printing.
In the case of the wet method, drying is performed thereafter. The drying temperature is, for example, 50 ℃ to 150 ℃, and the drying time is, for example, 1 minute to 10 minutes.
Examples of the dry method include chemical vapor deposition methods such as a thermal chemical vapor deposition method and a photochemical vapor deposition method.
Preferably, a wet method is used, and more preferably, a gravure coating method or a bar coating method is used.
Thus, as shown in fig. 1, an antireflection glass 1 having a glass substrate 2, an antireflection layer 3, and an antifouling layer 4 in this order was obtained.
In the above step, the sheet may be wound around a winding roll in forming each layer. Alternatively, the antireflection layer 3 and the antifouling layer 4 may be continuously formed until the formation thereof, and the antifouling layer 4 may be wound around a winding roll after the formation thereof.
If necessary, a protective film or the like may be laminated on the lower surface of the antireflection glass 1, and then wound in a roll shape together with the protective film.
The thickness of the obtained antireflection glass 1 is, for example, 10 μm or more, preferably 50 μm or more, and is, for example, 150 μm or less, preferably 100 μm or less.
The upper surface of the antireflection glass 1, that is, the upper surface of the antifouling layer 4 has a surface roughness Ra of less than 2.0nm, preferably 1.8nm or less. When the surface roughness is not more than the upper limit, the scratch resistance is excellent. The surface roughness Ra is, for example, 0.5nm or more, preferably 1.0nm or more. The surface roughness Ra is an arithmetic average roughness Ra and can be measured by an atomic force microscope (manufactured by Veeco Instruments inc., "Nanoscope 4").
The dynamic friction coefficient of the upper surface of the antireflection glass 1 is, for example, 0.10 or less. When the dynamic friction coefficient is not more than the above upper limit, the scratch resistance is excellent. The dynamic friction coefficient can be measured, for example, using an automatic friction and wear analysis device (manufactured by Kyowa interface science corporation, "TSf-503").
The scratch hardness (pencil method) of the upper surface of the antireflection glass 1 is preferably 7H or more. The scratch hardness can be measured in accordance with JIS K5600-5-4.
For the upper surface of the antireflection glass 1, the load in the steel wool resistance test is preferably 3kg/cm2The above. In the STEEL WOOL resistance test, STEEL WOOL (#0000, NIHON STEEL WOOL co., ltd) was rubbed on the upper surface of the antireflection glass 110 times in a reciprocating manner, and the measurement was performed, specifically, described in detail in examples.
The antireflection glass 1 preferably has transparency. Specifically, the total light transmittance (JIS K7375-.
3. Use of anti-reflection glass
The antireflection glass 1 is used in an optical device such as an image display device. When the image display device (specifically, an image display device having an image display element such as an LCD module or an organic EL module) includes the antireflection glass 1, the antireflection glass 1 is used as, for example, an outermost protective substrate.
The antireflection glass 1 is not an image display device, and is, for example, one member such as an outermost protective substrate provided in the image display device. That is, the antireflection glass 1 is a member used for manufacturing an image display device or the like, does not include an image display element such as an LCD module, and includes a glass substrate 2, an antireflection layer 3, and an antifouling layer 4, and is a commercially available device that is distributed as a member itself.
The antireflection glass 1 includes a glass substrate 2 and an antireflection layer 3 disposed on the upper surface of the glass substrate 2. Therefore, the antireflection glass 1 can suppress reflection of external light such as sunlight and indoor light on the upper surface of the antireflection glass 1. That is, reflection of external light can be suppressed.
Further, the surface roughness Ra of the upper surface of the antireflection glass 1 is less than 2.0 nm. Therefore, even when external factors such as pencil and steel wool are generated on the upper surface of the antireflection glass 1, the generation of interlayer peeling and damage of the antireflection glass 1 can be suppressed. Namely, the scratch resistance is excellent.
Since the glass substrate 2 has a thickness of 150 μm or less, the glass substrate 2 can be wound in a roll. Therefore, the production can be performed in a roll-to-roll manner, and the productivity is excellent.
Further, since the anti-staining layer 4 is provided on the upper surface of the anti-reflection layer 3, it is possible to prevent contaminants such as fingerprints and dust from adhering to the upper surface of the anti-reflection glass 1. Namely, excellent antifouling properties.
Further, since the antireflection layer 3 is in direct contact with the upper surface of the glass substrate 2, the antireflection layer 3 (preferably, an inorganic compound) has good adhesion to the glass substrate 2 and excellent abrasion resistance.
Therefore, an adhesion layer for improving adhesion is not required between the antireflection layer 3 and the glass substrate 2, and thus, a reduction in thickness and simplification of manufacturing can be achieved.
4. Modification example
A modification of the embodiment shown in fig. 1 will be described below. These modifications also exhibit the same operational advantages as the above-described embodiment.
In the embodiment shown in fig. 1, the antireflection glass 1 is provided with the stain-proofing layer 4, but for example, as shown in fig. 2, the antireflection glass 1 may not be provided with the stain-proofing layer 4. That is, the antireflection glass 1 may be composed of the glass substrate 2 and the antireflection layer 3. In this case, the surface roughness Ra of the upper surface of the antireflection layer 3 is measured to determine the surface roughness of the upper surface of the antireflection glass 1.
Preferably, from the viewpoint of antifouling property and protection of the antireflection layer 3, the embodiment shown in fig. 1 can be cited.
In the embodiment shown in fig. 1, the antireflection layer 3 is a 4-layer laminate, but the number of layers is not limited, and may be, for example, 1 to 3 layers or 5 or more. Preferably 2 or more and 6 or less, more preferably 4. The antireflection layer 3 may further include another refractive index layer such as an intermediate refractive index layer.
[ examples ]
The present invention will be described more specifically below with reference to examples and comparative examples. The present invention is not limited to the examples and comparative examples. Specific numerical values such as the blending ratio (content ratio), the physical property value, and the parameter used in the following description may be replaced with upper limit values (numerical values defined as "lower" and "less" or lower limit values (numerical values defined as "upper" and "more" or higher) or lower limit values (numerical values defined as "lower" and "more" of ") described in the above-mentioned" specific embodiment "in accordance with the blending ratio (content ratio), the physical property value, and the parameter described above.
Example 1
A glass substrate (alkali-free glass, thickness 100 μm, manufactured by Nippon Denko K.K.; "G-Leaf") elongated in one direction was introduced into a roll-to-roll sputtering film forming apparatus, and Nb was added to the glass substrate by a sputtering method while moving the glass substrate as shown in Table 12O5Layer and SiO2The layers were alternately formed to prepare an antireflection layer (4-layer laminate). In the formation of these layers, the amount of Ar introduced and the amount of Ar discharged were adjusted to control the sputtering film formation apparatusThe pressure in the film forming chamber (2) was kept constant at 0.25Pa, and the amount of oxygen introduced was adjusted by plasma emission monitoring control.
Next, a layer (thickness 2nm) comprising a fluorine-based resin was formed on the upper surface of the antireflection layer as an antifouling layer. The antifouling layer is formed as follows: a varnish prepared by diluting the fluorine-based resin to a concentration of 006 wt% was applied to the upper surface of the antireflection layer by a bar coating method, and dried at 60 ℃.
Thus, a roll of antireflection glass was obtained (see fig. 1).
Comparative example 1
An antireflection glass was produced in the same manner as in example 1, except that the air pressure in the film forming chamber was maintained at 1.0Pa to form an antireflection layer.
Comparative example 2
A cellulose triacetate film (TAC film, thickness 80 μm) with a hard coat layer (HC layer, thickness 6 μm) was prepared. The TAC film was introduced into a roll-to-roll sputtering film forming apparatus, and bombardment treatment (plasma treatment using Ar gas) was performed on the hard coat layer while the TAC film was moved. Thereafter, a 3.5nm Si layer was formed as an adhesion layer on the upper surface of the hard coat layer, and then Nb was alternately formed as shown in table 12O5Layer and SiO2And (3) a layer. Next, an antifouling layer was formed on the upper surface of the antireflection layer in the same manner as in example 1. Thus, the antireflection film of comparative example 2 was produced.
Comparative example 3
An antireflection film of comparative example 3 was produced in the same manner as in comparative example 2, except that the air pressure in the film forming chamber was maintained at 1.0Pa to form an antireflection layer.
(thickness)
The thicknesses of the antireflection layer and the antifouling layer in example 1 and each comparative example were measured using a scanning fluorescent X-ray analyzer (manufactured by Rigaku Corporation, "ZSX Primus II"). The thickness of the glass substrate and the TAC film was measured using a "direct thickness gauge (manufactured by PEACOCK," DG-205) ". The results are shown in Table 1.
(surface roughness)
The surface roughness Ra of the upper surface (surface of the antifouling layer) of the antireflection member (antireflection glass or antireflection film) of example 1 and each comparative example was measured using an atomic force microscope (product of Veeco Instruments inc., "Nanoscope 4"). The results are shown in Table 1.
(scratch hardness based on the Pencil method)
The scratch hardness of the upper surface of the antireflection member was measured in each example and each comparative example in accordance with JIS K5600-5-4. The results are shown in Table 1.
(Steel wool resistance test)
Using Steel Wool (SW) of #0000, the upper surface of the anti-reflection member of example 1 and each comparative example was set to 300g/cm2The load was rubbed back and forth 10 times. The transmitted light and the reflected light of the antireflection layer at this time were observed to confirm whether or not the antireflection member was damaged or delaminated. Next, the load was changed to be increased, and the occurrence of damage was confirmed in the same manner as described above. This operation was repeated until occurrence of damage could be confirmed, and the load at the time when damage or interlayer peeling occurred is shown in table 1. The load was varied up to 3kg/cm in 100g units2Up to 3kg/cm2In the case where no occurrence of damage or delamination was observed, the expression "3 kg/cm" was used2Above ". The results are shown in Table 1.
[ Table 1]
[ Table 1]
Figure BDA0002226237610000131
(examination)
The antireflection film of comparative example 1 had a pencil hardness of 6B and an SW resistance test of 300g/cm because the surface roughness was 2.0nm or more2. That is, even with a pencil having a very low hardness or a steel wool having a low load, damage and delamination occur. Namely, the scratch resistance was very low.
The antireflection glass of comparative example 2 had a pencil hardness of 3H and a SW resistance of 3kg/cm, since no glass substrate was used2. I.e. for hardIn particular, pencil and steel wool having a high load are damaged and have insufficient scratch resistance.
The antireflection film of comparative example 3 had a surface roughness of 2.0nm or more and no glass substrate, and therefore had a pencil hardness of 6B and a SW resistance of 300g/cm2. That is, even with a pencil having a very low hardness or a steel wool having a low load, damage and delamination occur. Namely, the scratch resistance is low.
On the other hand, the antireflection glass of example 1 had a surface roughness of less than 2.0nm and a glass substrate, and therefore had a pencil hardness of 7H or more and a SW resistance test of 3kg/cm2The above. That is, even when the pencil had a hardness as high as 7H, the load of the steel wool was set to 3kg/cm2Even when the load is high, the layers (glass substrate, antireflection layer, and antifouling layer) are not damaged. Further, although the adhesion layer is not formed, interlayer peeling at the interface between the glass substrate and the antireflection layer, etc. does not occur. Therefore, excellent scratch resistance is exhibited.
When comparative example 1 and comparative example 3 were compared, the pencil hardness and SW resistance were not improved at all and no improvement in scratch resistance was observed even when the TAC film was simply changed to a glass substrate as a substrate in the case where the surface roughness was 2.0nm or more. On the other hand, when the surface roughness is less than 2.0nm, the pencil hardness and the SW resistance are improved by using the glass substrate as the substrate for the first time, and it is found that the pencil hardness is 7H or more and the SW resistance test is 3kg/cm2The above-mentioned very high scratch resistance.

Claims (3)

1. An antireflection glass comprising:
a glass substrate,
And an antireflection layer disposed on one side in the thickness direction of the glass substrate,
the surface roughness Ra of the surface of the anti-reflection glass on one side in the thickness direction is less than 2.0 nm.
2. The antireflection glass according to claim 1, wherein a thickness of the glass substrate is 150 μm or less.
3. The antireflection glass according to claim 1 or 2, further comprising an antifouling layer disposed on one side in the thickness direction of the antireflection layer.
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