CN107235643B - Method for manufacturing high anti-reflection reinforced glass - Google Patents
Method for manufacturing high anti-reflection reinforced glass Download PDFInfo
- Publication number
- CN107235643B CN107235643B CN201710193714.2A CN201710193714A CN107235643B CN 107235643 B CN107235643 B CN 107235643B CN 201710193714 A CN201710193714 A CN 201710193714A CN 107235643 B CN107235643 B CN 107235643B
- Authority
- CN
- China
- Prior art keywords
- refractive index
- coating liquid
- silicon compound
- high refractive
- glass substrate
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B27/00—Tempering or quenching glass products
- C03B27/02—Tempering or quenching glass products using liquid
- C03B27/03—Tempering or quenching glass products using liquid the liquid being a molten metal or a molten salt
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/73—Anti-reflective coatings with specific characteristics
- C03C2217/734—Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Wood Science & Technology (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Surface Treatment Of Glass (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention relates to a method for producing a highly anti-reflection strengthened glass. Coating a glass substrate with a high refractive index coating liquid and a low refractive index coating liquid, heating the coated glass substrate at 100 to 500 ℃ to form an antireflection film, and chemically strengthening the antireflection film in a metal salt melt for ion exchange at 380 to 500 ℃; the coating liquid for high refractive index contains (a) a silicon compound, (b) inorganic oxide particles for high refractive index formed by zirconia and/or titania particles, and (c) a metal chelate compound, wherein the mass ratio of (a) to (b) is 50/50-95/5, and (c) is 20 parts by weight or less relative to 100 parts by weight of (a) and (b); the low refractive index coating liquid contains the hollow silica particles having voids in the interiors of the (a) and (d) and the (c), wherein the mass ratio of the (a) to the (d) is 50/50-99/1, and the (c) is 20 parts by weight or less relative to 100 parts by weight of the (a) and the (d) in total.
Description
Technical Field
The present invention relates to a method for producing a reinforced glass to which a high antireflection function is imparted by an antireflection film composed of a plurality of layers.
Background
Tempered glass having improved glass strength is widely used for window glass of automobiles and houses, and recently, is also used for a full-surface protective panel of a capacitive touch panel, a display screen of various mobile devices such as a digital camera and a mobile phone, and the like.
The latter tempered glass for display panels has a small and complicated shape, and requires shape processing such as cutting, end face processing, and hole forming. However, since it is difficult to perform these shape processing after the strengthening, the glass substrate is processed in advance into the final product shape and then subjected to the strengthening treatment.
As a method for strengthening glass, a physical strengthening method using rapid cooling and a chemical strengthening method using ion exchange are known, and the physical strengthening method is directed to glass having a thickness of several mm or more and is not effective for a glass substrate having a small thickness. Therefore, chemical strengthening is generally used for thin glass such as the above protective panels and display panels.
Among them, the chemical strengthening method by ion exchange is performed by replacing metal ions (for example, sodium ions) having a small ionic radius contained in glass with metal ions (for example, potassium ions) having a larger ionic radius. That is, a metal ion having a small ionic radius is replaced with a metal ion having a larger ionic radius, thereby forming a compressive stress layer on the glass surface.
As a result, when the glass is broken, a force for releasing the compressive stress on the surface is required in addition to a force for breaking the intermolecular bond, and the strength is remarkably improved as compared with a normal glass.
On the other hand, a reinforced glass reinforced by a chemical treatment using ion exchange is sometimes required to have an antireflection function or other functions, and particularly, an antireflection function is required for the above-mentioned protective panel, various display panels, and the like.
In order to impart an antireflection function, an antireflection film having a low refractive index may be formed on the surface. As means for forming such an antireflection film, there are known methods roughly classified into a method using vapor deposition and a method using a sol-gel method.
The vapor deposition method is not industrially implemented in many cases because it requires an extremely high cost apparatus. Currently, a sol-gel method of forming an antireflection film by applying a coating liquid containing fine particles and gelling by heat treatment is mainly used because of low production cost and high productivity.
As an antireflection film formed by such a sol-gel method, for example, an antireflection film containing a hydrolysis condensate of a silicon compound, a metal chelate compound, and low-refractive silica particles is known (see patent document 1).
However, there is a significant problem to be solved for forming an antireflection film on the surface of a strengthened glass obtained by chemical treatment.
As described above, the shape processing of the tempered glass is performed before the tempering treatment, and in the tempered glass by the chemical treatment, the formation of the antireflection film must be performed after the tempering treatment. This is because, after the formation of the antireflection film, potassium ions cannot penetrate into the glass, and therefore, the strengthening treatment cannot be performed.
However, since the shape processing is already performed before the strengthening treatment (chemical treatment by ion exchange), the formation of the antireflection film is performed after the shape processing of the glass. Therefore, even if the anti-reflective coating is formed by the sol-gel method with high productivity, the anti-reflective coating must be formed on the product after the shape processing one by one, so that the productivity is remarkably lowered, and the advantage of the sol-gel method that the large area processing can be performed is completely lost.
In order to solve the above problems, a method of forming an antireflection film and then performing glass strengthening by chemical treatment has been proposed.
One method is a method of strengthening glass by ion exchange using the interstitial spaces (hereinafter referred to as voids) between particles of inorganic fine particles contained in an antireflection film formed on the surface (patent document 2). However, this method has the following problems: the voids that enable ion exchange are difficult to control.
In order to solve the above problems, the following methods are proposed: hollow particles having a space inside are used without using gaps between the particles, and ion exchange is performed through the internal space (patent document 3). Since this method uses particles having a predetermined space volume, the conditions for ion exchange can be easily set as compared with the above-described void method. However, since there are a small number of types of hollow inorganic particles and industrial production methods are limited, there are a limited number of types of inorganic particles that can be used.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2002-221602
Patent document 2: japanese patent laid-open publication No. 2002-234754
Patent document 3: japanese patent laid-open publication No. 2011-88765
Disclosure of Invention
Problems to be solved by the invention
However, in order to improve the antireflection performance of the antireflection film, a two-layer structure in which a high refractive index layer is provided between a low refractive index layer and a glass substrate, rather than a one-layer structure of only the low refractive index layer, is required, and in order to further improve the performance of the antireflection film, a three-layer structure in which a medium refractive index layer is provided between a high refractive index layer and a glass substrate, is required.
However, in order to exhibit a predetermined refractive index, it is necessary to blend zirconia particles (refractive index 2.10) and titania particles (refractive index 2.72) having a refractive index higher than that of silica particles in the high refractive index layer and the medium refractive index layer.
However, since these high refractive index particles are difficult to obtain hollow particles, ion exchange using the internal space of the particles cannot be achieved, and when the antireflection layer has a two-layer structure or a three-layer structure among the above structures, it is difficult to perform a glass strengthening treatment using ion exchange after forming the antireflection layer under normal conditions and penetrating a plurality of layers.
The present inventors have intensively studied a method for strengthening a glass substrate having an antireflection film composed of a plurality of layers formed on the surface thereof by an ion exchange method using the internal space of hollow particles and the gaps between the particles, and as a result, have found that a glass substrate having a high antireflection function and strengthened can be obtained by controlling the composition and the curing conditions of the antireflection film and further controlling the ion exchange conditions (strengthening treatment conditions), and have completed the present invention.
Means for solving the problems
That is, the present invention provides a method for producing a highly anti-reflection strengthened glass,
the method comprises forming an antireflection film including at least a low refractive index layer having a refractive index of 1.45 or less on a viewing field side and a high refractive index layer having a refractive index of 1.55 or more and less than 2.00 on a glass substrate side on a surface of the glass substrate, and subjecting the glass substrate on which the antireflection film is formed to a chemical strengthening treatment by an ion exchange method to produce a high antireflection strengthened glass,
coating a glass substrate with a coating liquid for high refractive index, then coating a coating liquid for low refractive index, then heating at a temperature of 100-500 ℃ to form an antireflection film, and then performing chemical strengthening treatment in a metal salt melt for ion exchange at a temperature of 380-500 ℃;
the coating liquid for high refractive index contains:
(a) a silicon compound represented by the following formula (1),
Rn-Si(OR1)4-n (1)
in the formula (1), R is alkyl or alkenyl,
R1is an alkyl group or an alkoxyalkyl group,
n is an integer of 0 to 2;
(b) inorganic oxide particles for high refractive index formed of zirconia and/or titania particles; and the number of the first and second groups,
(c) a metal chelate compound, a metal chelate complex,
the mass ratio (a/b) of the silicon compound (a) to the inorganic oxide particles (b) for high refractive index is in the range of 50/50 to 95/5, and the metal chelate compound (c) is in the range of 20 parts by weight or less with respect to 100 parts by weight of the total amount of the silicon compound (a) and the inorganic oxide particles (b) for high refractive index;
the low refractive index coating liquid contains:
(a) a silicon compound represented by the above formula (1);
(d) hollow silica particles having a hollow inside; and the number of the first and second groups,
(c) a metal chelate compound, a metal chelate complex,
the mass ratio (a/d) of the silicon compound (a) to the hollow silica particles (d) is in the range of 50/50 to 99/1, and the metal chelate compound (c) is in the range of 20 parts by weight or less relative to 100 parts by weight of the total amount of the silicon compound (a) and the hollow silica particles (d).
In the invention of the method for producing a highly anti-reflection strengthened glass, it is preferable that:
1) the antireflection film further has a medium refractive index layer having a refractive index of 1.50 or more and less than 1.90 and a refractive index smaller than that of the high refractive index layer on the substrate side of the high refractive index layer,
coating a coating liquid for a medium refractive index before coating a coating liquid for a high refractive index, the coating liquid for a medium refractive index comprising:
(a) a silicon compound represented by the above formula (1);
(e) inorganic oxide particles for medium refractive index containing zirconia and/or titania particles; and the number of the first and second groups,
(c) a metal chelate compound, a metal chelate complex,
the mass ratio (a/e) of the silicon compound (a) to the inorganic oxide particles (e) for medium refractive index is 50/50-95/5, the amount of the metal chelate compound (c) is 20 parts by weight or less based on 100 parts by weight of the total amount of the silicon compound (a) and the inorganic oxide particles (b) for medium refractive index,
2) the silicon compound is tetraethoxysilane,
3) heating at a temperature of 200 to 300 ℃ to form an antireflection film,
4) performing chemical strengthening treatment at 380-480 ℃.
Further, there is provided a method for manufacturing a glass substrate, characterized in that the shape of the glass substrate is processed after the formation of the antireflection film and before the chemical strengthening treatment.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the method of the present invention, it is possible to industrially and extremely useful to glass-reinforce a glass substrate having a composite antireflection film in which a refractive index layer containing hollow silica particles having a cavity therein and a refractive index layer containing inorganic oxide particles having no cavity therein (hereinafter, also referred to as "intermediate inorganic oxide particles") are laminated by a single treatment after forming the antireflection film. As described above, the hollow silica particles and the solid inorganic oxide particles differ in the mechanism of glass strengthening by ion exchange, and thus it has been difficult to perform glass strengthening by a single process.
Further, in the present invention, since the antireflection film can be formed on the surface of the glass substrate to be the strengthened glass in the stage before the shape processing, the productivity is extremely high, and the strengthened glass product having the antireflection film on the surface of the strengthened glass can be manufactured at low cost. The obtained strengthened glass has a reduced minimum reflectance and excellent antireflection properties against light having a wide wavelength range because of having an antireflection film composed of a plurality of layers.
Such a strengthened glass product is suitably used for products having a thin glass substrate, for example, full-surface protective panels for capacitive touch panels, display panels for various mobile devices such as digital cameras and cellular phones, and the like.
Detailed Description
< formation of antireflection film >
In the present invention, when the antireflection film is composed of three layers, the medium refractive index layer, the high refractive index layer, and the low refractive index layer are laminated in this order, and the medium refractive index layer is in close contact with the glass substrate. When the antireflection film is composed of two layers, the intermediate refractive index layer is not present, and the high refractive index layer and the low refractive index layer are laminated in this order, and the high refractive index layer is in close contact with the glass substrate.
< glass substrate >
As the glass substrate, any of various compositions can be used as long as it has a composition capable of being strengthened by chemical strengthening treatment, but glass containing alkali metal ions and alkaline earth metal ions having a smaller ionic radius is suitable. For example, soda-lime silicate glass, alkali-containing aluminosilicate glass, alkali-containing borosilicate glass, and the like are suitable, and among these, glass containing sodium ions is most suitable. Most preferably, the glass contains 5% by weight or more of sodium ions.
The thickness of the glass substrate is not particularly limited, but is generally preferably in the range of 2mm or less in order to effectively perform chemical strengthening treatment described later.
< formation of Low refractive index layer >
The low refractive index layer has a refractive index of 1.45 or less, and is formed by coating a low refractive index coating liquid containing the following components, drying, and heating. That is, the low-refraction coating liquid is constituted by: comprises
(a) A silicon compound represented by the formula (1),
Rn-Si(OR1)4-n (1)
In the formula (1), R is alkyl or alkenyl,
R1is an alkyl group or an alkoxyalkyl group,
n is an integer of 0 to 2,
(d) hollow silica particles having voids therein, and
(c) a metal chelate compound, a metal chelate complex,
the mass ratio (a/d) of the silicon compound (a) to the hollow silica particles (d) is in the range of 50/50 to 99/1, and the metal chelate compound (c) is in the range of 20 parts by weight or less relative to 100 parts by weight of the total amount of the silicon compound (a) and the hollow silica particles (d).
(a) Silicon compounds
This component functions as a binder for forming a dense and high-strength film having good adhesion to a glass substrate, and is represented by the above formula (1).
Specific examples of the compound include silicon compounds in which n is 0, such as: tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane; examples of the silicon compound having n ═ 1 include: trialkoxysilanes such as methyltrimethoxy (ethoxy) silane, methyltriphenoxysilane, ethyltrimethoxy (ethoxy) silane, γ - (2-aminoethyl) aminopropyltrimethoxysilane, γ -methacryloxypropyltrimethoxysilane, γ -glycidoxypropyltrimethoxysilane and γ -mercaptopropyltrimethoxysilane; examples of the silicon compound having n-2 include: dialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, cyclohexylmethyldimethoxysilane, γ -chloropropylmethyldimethoxysilane, γ -glycidoxypropylmethyldimethoxysilane and γ -methacryloxypropylmethyldimethoxysilane.
In the present invention, among the above exemplified compounds, silicon compounds having n-0 and n-1 are particularly preferable from the viewpoint of strength retention, and among them, tetraethoxysilane and γ -glycidoxypropyltrimethoxysilane are most preferable because they can form a dense and high-strength film connected in a three-dimensional network.
(d) Hollow silica particles
The particles made of silica having a cavity therein are usually fine hollow particles having a particle diameter (average particle diameter on a volume basis measured by a laser diffraction scattering method) of 5 to 150nm and a shell layer thickness of about 1 to 15 nm. The component is a component necessary for forming a layer having a refractive index of 1.45 or less and exhibiting excellent antireflection ability, although it is ion-exchanged by the internal cavity. Therefore, it is preferable to select hollow silica particles having a refractive index in the range of 1.20 to 1.38.
It is known that such hollow silica particles (d) are usually sold in a dispersion liquid state dispersed in a lower alcohol such as methanol, ethanol, propanol, etc., for example, in Japanese patent laid-open No. 2001-233611, etc., and therefore, commercially available products are preferably obtained and used.
The mass ratio (a/d) of the silicon compound (a) to the hollow silica particles (d) is required to be 50/50-99/1.
The lower limit value [1] of the hollow silica particles in the composition of both is determined from the viewpoint of ease of ion exchange and reinforcement, and the upper limit value [50] is determined from the viewpoint of the abrasion resistance of the low refractive index layer and the adhesion to the high refractive index layer. That is, when the lower limit value is lower than the lower limit value, effective chemical strengthening treatment cannot be performed, and when the upper limit value is higher than the lower limit value, the mechanical strength of the low refractive index layer is lowered and peeling from the high refractive index layer is easy. From the above viewpoint, the mass ratio (a/d) is preferably 80/20 to 98/2.
(c) Metal chelate compounds
The component has a function as a crosslinking agent, and the antireflection film formed is made denser, and the decrease in strength and hardness of the film caused by the blending of the hollow silica sol is effectively suppressed.
The metal chelate compound (c) is a compound in which a chelating agent represented by a bidentate ligand is coordinated to a metal such as titanium, zirconium or aluminum.
Specifically, there may be mentioned: titanium chelate compounds such as triethoxymono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, monoethoxytris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxymono (ethylacetoacetate) titanium, diethoxybis (ethylacetoacetate) titanium, monoethoxytris (ethylacetoacetate) titanium, mono (acetylacetonato) tris (ethylacetoacetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, and tris (acetylacetonato) mono (ethylacetoacetate) titanium;
zirconium chelate compounds such as triethoxymono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, monoethoxytris (acetylacetonato) zirconium, tetrakis (acetylacetonato) zirconium, triethoxymono (ethylacetoacetate) zirconium, diethoxybis (ethylacetoacetate) zirconium, monoethoxytris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) zirconium, and tris (acetylacetonato) mono (ethylacetoacetate) zirconium;
aluminum chelates such as diethoxymono (acetylacetonate) aluminum, monoethoxybis (acetylacetonate) aluminum, diisopropoxymono (acetylacetonate) aluminum, monoethoxybis (ethylacetoacetate) aluminum, diethoxymono (ethylacetoacetate) aluminum, and the like.
The metal chelate compound (c) is 20 parts by weight or less, preferably 0.01 to 20 parts by weight, and particularly preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total amount of the silicon compound (a) and the hollow silica particles (d). When the amount is too large, a metal chelate compound precipitates in the antireflection film, and appearance is deteriorated. When the amount of the anti-reflective coating is small, the strength and hardness of the anti-reflective coating are reduced, and the effectiveness of the chemical strengthening treatment of the glass substrate is not preferable.
The low refractive index coating liquid is generally used by dissolving or dispersing the essential components in an organic solvent for easy coating. Representative of the possible uses: alcohol solvents such as methanol, ethanol, isopropanol, ethyl cellosolve, and ethylene glycol; ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as acetone and methyl ethyl ketone; aromatic solvents such as toluene and xylene. Particularly, an alcohol solvent is preferably used.
The amount of the organic solvent used may be such that the viscosity of the coating liquid for low refraction is within a range suitable for coating without causing sagging. In general, the organic solvent may be used in an amount to give a total solid content concentration of 0.1 to 20% by weight based on the total weight. Since the hollow silica particles (d) are sold as being dispersed in a dispersion medium such as an alcohol solvent, the amount of the organic solvent is a value including the amount of the dispersion medium.
Further, in order to promote hydrolysis and condensation of the silicon compound (a), an aqueous acid solution such as an aqueous hydrochloric acid solution may be added in an appropriate amount to the low-refraction coating liquid.
The low refractive index coating liquid is applied to a high refractive index layer described later and dried, and then heated to form a low refractive index layer, and heat treatment by heating is usually performed once after each layer is applied and dried.
The coating method is not particularly limited, and a method such as a dip coating method, a roll coating method, a die coating method, a flow coating method, or a spray method can be used.
< formation of high refractive index layer >
The high refractive index layer has a refractive index of 1.55 or more and less than 2.00, and is formed by applying a high refractive index coating liquid containing the following components, drying, and heating. That is, the high refractive coating liquid is constituted by: comprises
(a) A silicon compound represented by the above formula (1),
(b) Inorganic oxide particles for high refractive index formed from zirconia and/or titania particles, and
(c) a metal chelate compound, a metal chelate complex,
the mass ratio (a/b) of the silicon compound (a) to the inorganic oxide particles (b) for high refractive index is 50/50-95/5, and the metal chelate compound (c) is 20 parts by weight or less based on 100 parts by weight of the total amount of the silicon compound (a) and the inorganic oxide particles (b) for high refractive index.
The silicon compound (a) and the metal chelate compound (c) used in the high refractive coating liquid may be the same as those exemplified above for the low refractive coating liquid.
(b) Inorganic oxide particles for high refractive index
The inorganic oxide particles for high refractive index are suitably determined and used as follows: zirconia particles having a refractive index of 2.10 and no cavity inside and titania particles having a refractive index of 2.72 and no cavity inside are used alone or mixed so that the high refractive index layer becomes a layer having a refractive index of 1.55 or more and less than 2.00.
The mass ratio (a/b) of the silicon compound (a) to the inorganic oxide particles for high refraction (b) is required to be 50/50-95/5.
The lower limit value [5] of the high refractive inorganic oxide particles in the mixture ratio of the both is determined from the viewpoint of easy ion exchange and reinforcement, and an amount larger than that of the hollow silica is required to form the inter-particle voids. The upper limit value [50] is determined from the viewpoint of the abrasion resistance of the obtained high refractive index layer and the adhesion to the glass substrate. That is, when the refractive index is lower than the lower limit value, effective chemical strengthening treatment cannot be performed, and when the refractive index is higher than the upper limit value, the mechanical strength of the high refractive index layer is lowered and the high refractive index layer is easily peeled from the glass substrate. From the above viewpoint, the mass ratio (a/b) is preferably 55/45 to 90/10.
Since the inorganic oxide particles (b) for high refractive index are usually distributed as dispersed in a dispersion medium such as an alcohol solvent, it is necessary to consider the dispersion medium as an organic solvent in a coating liquid, similarly to the hollow silica particles (d).
(c) Metal chelate compounds
The metal chelate compound (c) may use the same metal chelate compound as in the low refractive index layer. The amount of the compound is the same as the above.
As the high refractive coating liquid, an organic solvent or an aqueous acid solution can be suitably used as well as the low refractive coating liquid. The same method can be used for coating on the glass substrate, but the dip coating method is preferable.
< formation of Medium refractive index layer >
When the antireflection film is composed of three layers, a medium refractive index layer having a refractive index of 1.50 or more and less than 1.90 is provided between the high refractive index layer and the glass substrate. The refractive index of the medium refractive index layer needs to be smaller than the refractive index of the high refractive index layer stacked thereon.
The medium refractive index layer is constituted by: comprises a coating liquid for high refraction containing the following components,
(a) a silicon compound represented by the above formula (1),
(e) Inorganic oxide particles for medium refractive index formed of zirconia and/or titania particles, and
(c) a metal chelate compound, a metal chelate complex,
the mass ratio (a/e) of the silicon compound (a) to the inorganic oxide particles (e) for medium refractive index is 50/50-95/5. The mass ratio (a/e) is preferably 55/45-90/10.
The range of the mass ratio (a/e) and the reason for limiting the range are based on the range of the high refractive index layer and the reason for limiting the range. The same method is also used for coating on a glass substrate using a metal chelate (c), an organic solvent, and an aqueous acid solution as appropriate, based on a low-refractive coating liquid, but a dip coating method is preferred.
The silicon compound (a), the inorganic oxide particles for intermediate refractive index (e) composed of zirconia and/or titania particles, and the metal chelate compound (c) used in the coating liquid for intermediate refractive index may be used as they are in the coating liquid for high refractive index, and the range of the refractive index of the layer for intermediate refractive index (e) composed of zirconia and/or titania particles and the refractive index thereof are determined in consideration of the range of the refractive index and the refractive index thereof are smaller than those of the layer for high refractive index. The dispersion medium of the inorganic oxide particles (e) for intermediate refractive index also needs to be considered as an organic solvent.
< formation of antireflection film on glass substrate >
When the antireflection film has a two-layer structure, a high refractive index coating liquid is applied and dried on the glass substrate, a low refractive index coating liquid is applied and dried, and then heat treatment by heating is performed to cure and bake the glass substrate. When the antireflection film has a three-layer structure, the intermediate refractive coating liquid is applied and dried before the high refractive coating liquid is applied.
The drying treatment is not particularly limited, and is usually carried out at a temperature of 70 to 100 ℃ for about 0.5 to 1 hour.
In the present invention, the heating condition to be carried out at a time after drying is extremely important, and it is necessary to carry out the curing and baking treatment by heating in the range of 100 to 500 ℃. When the heating is carried out at a temperature of less than 100 ℃, the hydrolysis of the silicon compound (a) and the condensation of the metal chelate compound incorporated therein are not sufficiently carried out, and an antireflection film having a sufficient strength cannot be formed. When the temperature exceeds 500 ℃, hydrolysis and condensation progress excessively, the silicon compound (a) becomes almost completely a silica component, and ion exchange through the anti-reflection layer, which will be described later, is not performed, and the strengthening treatment becomes difficult. For this reason, the heating is particularly preferably 200 to 300 ℃.
The thickness of each layer of the obtained antireflection film is usually in the range of 50 to 150nm from the viewpoint of antireflection performance and ion exchange. Further, the thickness of each layer is preferably set to be in the range of 70 to 100 nm.
(processing of shape)
According to the above method, the substrate having the strong antireflection film formed on the glass substrate is subjected to shape processing according to the application, for example, mechanical processing such as cutting, edge face processing, and hole forming, before the chemical strengthening treatment. That is, this is because it is difficult to perform such machining after a glass substrate is made into a tempered glass by performing a chemical tempering treatment. By the shape processing, the glass substrate provided with the antireflection film is formed into a final product shape.
Chemical intensive treatment
The substrate having a strong antireflection film formed on a glass substrate is subjected to chemical strengthening treatment after the shape processing is performed. By replacing metal ions having a small ionic radius contained in the glass substrate with metal ions having a large ionic radius, a compressive stress layer is formed on the surface, and the glass substrate is strengthened. Thus, a strengthened glass product having an antireflection film on the surface can be obtained.
Specifically, the chemical strengthening treatment is carried out by bringing a glass substrate having an antireflection film into contact with an ion-exchange metal salt melt containing large metal ions by dipping or the like, thereby replacing the small metal ions in the glass substrate with the large metal ions. For example, a glass substrate containing sodium ions is brought into contact with a potassium salt melt (ion-exchange metal salt melt) such as potassium nitrate, whereby sodium ions having a small ionic radius are replaced with potassium ions having a large ionic radius, thereby forming a strengthened glass having high strength.
In the present invention, since there is an antireflection layer containing zirconia particles and titania particles having no internal space in addition to an antireflection layer containing hollow silica particles, it is important to control the heating temperature in the metal salt melt in order to perform ion exchange by penetrating both layers, and it is necessary to perform the control in the range of 380 to 500 ℃. At temperatures below 380 ℃, potassium nitrate does not melt sufficiently, and ion exchange becomes insufficient. Above 500 ℃, potassium nitrate starts to decompose, and therefore chemical strengthening treatment involves a risk. Therefore, the temperature is preferably in the range of 380 ℃ to 480 ℃. The treatment time is usually about 3 to 16 hours.
The high anti-reflection reinforced glass obtained by the present invention is not limited to the above layer structure. For example, an overcoat (overcoat layer) may be provided on the surface of the antireflection film to protect the antireflection film. Examples of such a top coat layer include an organopolysiloxane material and a fluororesin-based coating layer that impart abrasion resistance and scratch resistance.
Further, an adhesive layer formed of an acrylic, rubber, or silicone adhesive may be provided on the back side of the glass substrate. Further, the antireflection film of the present invention may be formed on the front surface and the back surface of the glass substrate.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples at all. In addition, not all combinations of the features described in the embodiments are essential to the solution of the present invention.
The various components and abbreviations used in the following examples and comparative examples, and the test methods are as follows.
(a) Silicon compounds
TEOS: tetraethoxysilane
(b) (e) inorganic oxide particles
ZrO2And (3) particle: zirconia particles (average particle diameter: 61.9nm, solid content: 30 wt%, dispersion solvent: methanol, refractive index: 2.40)
TiO2And (3) particle: titanium dioxide particles (average particle diameter: 108.8nm, solid content: 15 wt%, dispersion solvent: methanol, refractive index: 2.71)
(c) Metal chelate compounds
AlAA: aluminum monoacetylacetonate bis (ethylacetoacetate)
(d) Hollow silica particles
Average particle size: 40nm, refractive index: 1.25 (use of a silica sol containing 20% by weight of solid content and isopropyl alcohol as a dispersion solvent)
(f) Others
Solvent: isopropanol (IPA)
Hydrolysis catalyst: 0.05N hydrochloric acid
Glass substrate: soda-lime glass plate (50 mm. times.90 mm. times.1.1 mm)
(1) Light reflectivity
The minimum reflectance was measured by using a "V-570" testing machine manufactured by Nippon spectral Co., Ltd.
(2) Surface hardness
1kg/cm of steel wool #0000 was applied on one side2The surface of the test piece was rubbed with a load in a reciprocating manner by 20 cycles (1 cycle/second, distance 45mm/1 cycle), and whether or not scratches were formed on the surface of the antireflection film was visually observed, and the evaluation was performed according to the following criteria.
Good: no change in the antireflection film was observed
And (delta): there was linear scratches, but peeling of the antireflection film itself was not observed
X: the peeling of the antireflection film was confirmed
(3) Measurement of compressive stress value (glass Strength)
The larger the values of the surface stress CS (MPa) and the stress layer depth DOL (μm) ZCS and DOL due to the difference in refractive index (due to ion substitution) of the surface of the chemically strengthened glass, the larger the degree of strengthening, were measured by using "FSM-6000 LE" manufactured by atomic deposition (Czochralski) method. In the case of reinforcing soda-lime glass, the glass can sufficiently function as a tempered glass as long as the DOL value is about 10 μm.
Example 1
A low-refraction coating liquid and a high-refraction coating liquid having the following compositions were prepared.
Coating liquid for low refraction:
mixing at room temperature.
Coating liquid for high refraction:
mixing at room temperature.
First, the high refractive coating liquid was applied to a glass substrate (soda-lime glass) by a dip coating method, and dried at 100 ℃ for 0.5 hour. Next, the coating liquid for low refraction was applied in the same manner and dried at 100 ℃ for 0.5 hour. Then, the resultant was heated at 300 ℃ for 2 hours to form an antireflection film composed of two layers (curing, baking).
Then, the glass substrate with the antireflection film formed thereon was immersed in molten potassium nitrate at 390 ℃ for 16 hours, and subjected to a chemical strengthening treatment to obtain a high antireflection strengthened glass.
5 of the glass samples were prepared, and the light reflectance, glass strength and surface hardness were evaluated by the methods described above, and the results are shown in table 1 together with the composition of the coating liquid (anti-reflection film). The light reflectance and the glass strength are shown as an average of 5 samples.
Examples 2 to 6
A high anti-reflection strengthened glass was produced in the same manner as in example 1, except that the low refractive coating liquid and the high refractive coating liquid having the compositions shown in table 1 were used, and the measurement was performed in the same manner. The results are shown in Table 1.
Example 7
High anti-reflection reinforced glass was produced and measured in the same manner as in example 2, except that the glass was immersed at 450 ℃ for 4 hours to perform chemical reinforcing treatment. The results are shown in Table 1.
Example 8
High anti-reflection reinforced glass was produced and measured in the same manner as in example 5, except that the glass was immersed at 450 ℃ for 4 hours to perform chemical reinforcing treatment. The results are shown in Table 1.
Example 9
High anti-reflection reinforced glass was produced and measured in the same manner as in example 5, except that the glass was heated at 150 ℃ for 2 hours to form an anti-reflection film. The results are shown in Table 1.
[ Table 1]
Example 10
High anti-reflection reinforced glass was produced and measured in the same manner as in example 5, except that the glass was heated at 450 ℃ for 2 hours to form an anti-reflection film. The results are shown in Table 2.
Example 11
A low-refraction coating liquid and a high-refraction coating liquid having the following compositions were prepared.
Coating liquid for low refraction:
mixing at room temperature.
Coating liquid for high refraction:
mixing at room temperature.
In the same manner as in example 1, a high refractive index coating solution and a low refractive index coating solution were applied in this order on a glass substrate and dried, and then heated at 500 ℃ for 2 hours to form an antireflection film, and then immersed in molten potassium nitrate at 390 ℃ for 16 hours to perform a chemical strengthening treatment, thereby obtaining a high antireflection strengthened glass. The results are shown in Table 2.
Comparative examples 1 to 3
The same treatment as in example 1 was performed using the high-refractive coating liquid and the low-refractive coating liquid having the compositions shown in table 1, and the production of a high-anti-reflection strengthened glass was attempted.
In comparative example 1, the content of the zirconia grains in the high-refraction coating liquid was set to an amount exceeding the upper limit of the range of the present invention. In comparative example 2, the formation (curing, baking) temperature of the antireflection film was 550 ℃, and in comparative example 3, the formation temperature was 600 ℃. The results are shown in Table 2.
In comparative examples 2 and 3, neither CS nor DOL was measurable, and it was found that glass strengthening was not achieved.
[ Table 2]
Example 12
A high anti-reflection reinforced glass having a three-layer anti-reflection film was produced in the same manner as in example 1 except that in example 1, a high refractive coating liquid and a medium refractive coating liquid having the following compositions were used, and the medium refractive coating liquid was applied under the same conditions and dried before the high refractive coating liquid was applied, and the measurement was performed in the same manner. The results are shown in Table 3. It was found that even in the case of a glass substrate on which an antireflection film composed of three layers was formed, sufficient glass strengthening was performed by the method of the present invention.
Coating liquid for high refraction:
mixing at room temperature.
Coating liquid for intermediate refraction:
mixing at room temperature.
[ Table 3]
Claims (5)
1. A method for producing a highly anti-reflection strengthened glass,
the method comprises forming an antireflection film including at least a low refractive index layer having a refractive index of 1.45 or less on a viewing field side and a high refractive index layer having a refractive index of 1.55 or more and 1.69 or less on a glass substrate side on a surface of the glass substrate, and subjecting the glass substrate on which the antireflection film is formed to a chemical strengthening treatment by an ion exchange method to produce a high antireflection strengthened glass,
coating a glass substrate with a coating liquid for high refractive index, then coating a coating liquid for low refractive index, then heating at a temperature of 200-300 ℃ to form an antireflection film, and then performing chemical strengthening treatment in a metal salt melt for ion exchange at a temperature of 380-500 ℃;
the coating liquid for high refractive index contains:
(a) a silicon compound represented by the following formula (1),
Rn-Si(OR1)4-n (1)
in the formula (1), R is alkyl or alkenyl,
R1is an alkyl group or an alkoxyalkyl group,
n is an integer of 0 to 2;
(b) inorganic oxide particles for high refractive index formed of zirconia and/or titania particles; and the number of the first and second groups,
(c) a metal chelate compound, a metal chelate complex,
the mass ratio (a/b) of the silicon compound (a) to the inorganic oxide particles (b) for high refractive index is in the range of 50/50-95/5, the metal chelate compound (c) is in the range of 20 parts by weight or less relative to 100 parts by weight of the total amount of the silicon compound (a) and the inorganic oxide particles (b) for high refractive index,
the low refractive index coating liquid contains:
(a) a silicon compound represented by the formula (1);
(d) hollow silica particles having a hollow inside; and the number of the first and second groups,
(c) a metal chelate compound, a metal chelate complex,
the mass ratio (a/d) of the silicon compound (a) to the hollow silica particles (d) is in the range of 50/50-99/1, and the metal chelate (c) is in the range of 20 parts by weight or less relative to 100 parts by weight of the total amount of the silicon compound (a) and the hollow silica particles (d).
2. The method for producing a highly antireflection reinforced glass according to claim 1, wherein the antireflection film further has a medium refractive index layer having a refractive index of 1.55 or more and less than 1.69 and a refractive index smaller than that of the high refractive index layer on the glass substrate side of the high refractive index layer,
coating the intermediate refractive index coating liquid before coating the high refractive index coating liquid,
the coating liquid for medium refractive index contains:
(a) a silicon compound represented by the formula (1);
(e) inorganic oxide particles for medium refractive index formed of zirconia and/or titania particles; and the number of the first and second groups,
(c) a metal chelate compound, a metal chelate complex,
the mass ratio (a/e) of the silicon compound (a) to the inorganic oxide particles (e) for medium refractive index is in the range of 50/50-95/5, and the metal chelate compound (c) is in the range of 20 parts by weight or less with respect to 100 parts by weight of the total amount of the silicon compound (a) and the inorganic oxide particles (e) for medium refractive index.
3. The method for producing a highly antireflection reinforced glass according to claim 1 or 2, wherein the silicon compound is tetraethoxysilane.
4. The method for producing a highly antireflection reinforced glass according to claim 1, wherein the chemical reinforcing treatment is performed at a temperature of 380 to 480 ℃.
5. The method for producing a highly anti-reflection strengthened glass according to claim 1, wherein the shape of the glass substrate is processed after the anti-reflection film is formed and before the chemical strengthening treatment.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016063685A JP6606451B2 (en) | 2016-03-28 | 2016-03-28 | Manufacturing method of high antireflection tempered glass |
| JP2016-063685 | 2016-03-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107235643A CN107235643A (en) | 2017-10-10 |
| CN107235643B true CN107235643B (en) | 2022-04-05 |
Family
ID=59984040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710193714.2A Active CN107235643B (en) | 2016-03-28 | 2017-03-28 | Method for manufacturing high anti-reflection reinforced glass |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP6606451B2 (en) |
| CN (1) | CN107235643B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019202942A1 (en) * | 2018-04-19 | 2019-10-24 | フクビ化学工業株式会社 | Antireflective plate |
| JPWO2023026670A1 (en) * | 2021-08-23 | 2023-03-02 | ||
| WO2023063221A1 (en) * | 2021-10-12 | 2023-04-20 | フクビ化学工業株式会社 | Optical member |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1950197A (en) * | 2004-04-06 | 2007-04-18 | 帝人杜邦薄膜日本有限公司 | Antireflective film |
| CN101772470A (en) * | 2007-08-03 | 2010-07-07 | 日本电气硝子株式会社 | Hardened glass substrate and method for manufacturing the same |
| CN102574735A (en) * | 2009-10-20 | 2012-07-11 | 福美化学工业株式会社 | Method for producing antireflection reinforced glass |
| CN104118994A (en) * | 2013-04-23 | 2014-10-29 | 旭硝子株式会社 | Glass substrate with reflective films on both sides, and process for its production |
| CN103842856B (en) * | 2011-08-01 | 2015-12-02 | 福美化学工业株式会社 | Antireflection film and antireflection plate |
| WO2016037753A1 (en) * | 2014-09-12 | 2016-03-17 | Schott Ag | Method for producing a coated, chemically prestressed glass substrate having anti-fingerprint properties, and the produced glass substrate |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4100863B2 (en) * | 2000-10-23 | 2008-06-11 | 触媒化成工業株式会社 | Photoelectric cell |
| WO2011149694A1 (en) * | 2010-05-26 | 2011-12-01 | Corning Incorporated | Ion-exchanging an ar coated glass and process |
| JP2014091743A (en) * | 2012-10-31 | 2014-05-19 | Olympus Corp | Coating material, optical coating film and optical element |
| JP2017132644A (en) * | 2014-06-06 | 2017-08-03 | 旭硝子株式会社 | Chemically strengthened glass sheet with functional film, manufacturing method, and article thereof |
-
2016
- 2016-03-28 JP JP2016063685A patent/JP6606451B2/en active Active
-
2017
- 2017-03-28 CN CN201710193714.2A patent/CN107235643B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1950197A (en) * | 2004-04-06 | 2007-04-18 | 帝人杜邦薄膜日本有限公司 | Antireflective film |
| CN101772470A (en) * | 2007-08-03 | 2010-07-07 | 日本电气硝子株式会社 | Hardened glass substrate and method for manufacturing the same |
| CN102574735A (en) * | 2009-10-20 | 2012-07-11 | 福美化学工业株式会社 | Method for producing antireflection reinforced glass |
| CN103842856B (en) * | 2011-08-01 | 2015-12-02 | 福美化学工业株式会社 | Antireflection film and antireflection plate |
| CN104118994A (en) * | 2013-04-23 | 2014-10-29 | 旭硝子株式会社 | Glass substrate with reflective films on both sides, and process for its production |
| WO2016037753A1 (en) * | 2014-09-12 | 2016-03-17 | Schott Ag | Method for producing a coated, chemically prestressed glass substrate having anti-fingerprint properties, and the produced glass substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107235643A (en) | 2017-10-10 |
| JP2017178634A (en) | 2017-10-05 |
| JP6606451B2 (en) | 2019-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5433372B2 (en) | Method for producing antireflection tempered glass | |
| KR101887245B1 (en) | Inorganic oxide coating | |
| CN107235643B (en) | Method for manufacturing high anti-reflection reinforced glass | |
| KR101519497B1 (en) | Anti-reflective film having improved scratch-resistant and manufacturing method thereof | |
| JPWO2015041257A1 (en) | Tempered glass plate with low reflection film and method for producing the same | |
| EP3658517B1 (en) | Multi-layer antireflective coated articles | |
| EP2592119A2 (en) | Antireflection film and method for manufacturing same | |
| WO2015115492A1 (en) | Glass plate with anti-glare function for solar cells | |
| EP2907840A1 (en) | Optical article comprising a hard coat, and production method | |
| CN104335077A (en) | Optical element and optical element manufacturing method | |
| EP3558884B1 (en) | Anti-reflective coated articles and method of making them | |
| JP5471825B2 (en) | Heat ray reflective laminate and heat ray reflective layer forming coating solution | |
| JP2008046392A (en) | Method of manufacturing plastic optical article | |
| JPH095679A (en) | Plastic lens for spectacles | |
| CN117425632A (en) | Anti-reflection glass | |
| ES2936628T3 (en) | coated substrate | |
| EP3873862A1 (en) | Coated substrate | |
| CN117776546A (en) | Anti-reflection glass | |
| WO2019162847A1 (en) | Anti-fouling, multi-layer coated sapphire articles | |
| JP2004210573A (en) | Manufacturing method of glass with iron oxide film | |
| JP2007086413A (en) | Manufacturing method of plastic lens, composition for hard coat and plastic lens |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |