CN103476726B - With the sheet glass of low-reflection film - Google Patents
With the sheet glass of low-reflection film Download PDFInfo
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- CN103476726B CN103476726B CN201280016572.8A CN201280016572A CN103476726B CN 103476726 B CN103476726 B CN 103476726B CN 201280016572 A CN201280016572 A CN 201280016572A CN 103476726 B CN103476726 B CN 103476726B
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- 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
- C03C17/25—Oxides by deposition from the liquid phase
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
- C03C1/008—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route for the production of films or coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
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- 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
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/213—SiO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/45—Inorganic continuous phases
- C03C2217/452—Glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/465—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific shape
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- 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
- C03C2217/76—Hydrophobic and oleophobic coatings
-
- 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
- C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Composite Materials (AREA)
- Dispersion Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Laminated Bodies (AREA)
- Liquid Crystal (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
The present invention relates to a kind of sheet glass (10) with low-reflection film, it it is the sheet glass (10) with low-reflection film of the individual layer low-reflection film (14) having on the surface of sheet glass (12) and comprising matrix and hollow minute particle, the minimum reflectivity of the low-reflection film (14) within the scope of wavelength 300��1200nm is below 1.7%, the water contact angle on low-reflection film (14) surface is more than 97 ��, the oleic acid contact angle on low-reflection film (14) surface is more than 50 ��, and the oleic acid on low-reflection film (14) surface tumbles angle below 25 ��. Pass through the present invention, it may be possible to provide glass pane surface has the sheet glass with low-reflection film of the individual layer low-reflection film that reflectivity is enough low and greasy soils removability is good, the manufacture method that can manufacture the described sheet glass with low-reflection film and has the display unit of the described sheet glass with low-reflection film.
Description
Technical field
The present invention relates to the sheet glass with low-reflection film, the manufacture method of sheet glass with low-reflection film, display unit and the sheet glass with low-reflection film for display unit.
Background technology
The surface of sheet glass has the cover glass etc. being used as the cover glass of solar cell, various indicating meter and front plate, various window glass or touch-screen with the sheet glass of low-reflection film of low-reflection film.
At mobile phone or carry the various display unit of giant display or touch-screen etc. of the small-sized indicating meter of intelligent terminal etc., various televisors etc.; in order to improve aesthetics while protection indicating meter, use cover glass (protective glass) more and more in the front of display unit. So, in order to promote the visuognosis degree of the image shown by display unit, it may also be useful to the sheet glass with low-reflection film with anti-visible ray reflectance coating is as cover glass.
Wherein, the sheet glass with low-reflection film for various indicating meter, window glass for automobile, touch-screen etc. or the aforementioned sheet glass with low-reflection film for aforementioned display frequently are contacted by staff, it is desired to have the removability of the greasy soils of fingerprint etc.
As giving with the sheet glass of low-reflection film with the method for greasy soils removability, that is widely known by the people has the method attaching the film preventing greasy soils on its surface or the method (patent documentation 1) of coating anti-pollution layer on anti-reflection layer.
But, when the surface of the sheet glass with low-reflection film attaches the film preventing greasy soils, owing to increasing the operation such as the manufacturing process of film, the attaching operation of film, produce productivity and reduce, cause exterior quality decline because attaching inequality or the problem of cost increase etc. along with film attaching. And on anti-reflection layer when coating anti-pollution layer, also produce the problem of productivity decline etc.
Prior art literature
Patent documentation
The special table 2002-506887 publication of patent documentation 1 Japanese Patent
Summary of the invention
Invent technical problem to be solved
The present invention provide that a kind of reflectivity is enough low and greasy soils removability is good, the surface of sheet glass has the sheet glass with low-reflection film of individual layer low-reflection film, can manufacture the manufacture method of the described sheet glass with low-reflection film and has the display unit of the described sheet glass with low-reflection film.
The technical scheme that technical solution problem adopts
The present invention's is the sheet glass with low-reflection film on the surface of sheet glass with the individual layer low-reflection film comprising matrix and hollow minute particle with the sheet glass of low-reflection film, wherein, the minimum reflectivity of the described low-reflection film within the scope of wavelength 300��1200nm is below 1.7%, the water contact angle on described low-reflection film surface is more than 97 ��, the oleic acid contact angle on described low-reflection film surface is more than 50 ��, and the oleic acid on described low-reflection film surface tumbles angle below 25 ��.
Represent above-mentioned numerical range "��" use to comprise the numerical value recorded before and after it as the implication of lower value and higher limit, as long as being not particularly limited, below in this specification sheets "��" all use with identical meanings.
In the sheet glass with low-reflection film of the present invention, individual layer low-reflection film refers to the film of the homogeneous giving low reflection function or a substantially Rotating fields of homogeneous or heterogeneity. In addition, the sheet glass having low-reflection film of the present invention means that described low-reflection film is formed at the outermost sheet glass at least one party surface of sheet glass. Therefore, glass surface in the opposition side not forming described low-reflection film of the described sheet glass with low-reflection film or be formed at the lower floor of outermost low-reflection film, can form the conducting film of a layer and even multilayer, near infrared ray blocking film, anti electromagnetic wave film, hue adjustment film, binding property improve film, weather resistance improves film, electrostatic prevention film, other various required functional membrane.
The ratio of the fluorine element on the described low-reflection film surface preferably measured by X-ray photoelectron spectroscopy is 3��20 atom %.
The arithmetic average roughness (Ra) on the described low-reflection film surface preferably measured by scanning type probe microscope device is 3.0��5.0nm.
The specific refractory power of preferred described low-reflection film is 1.30��1.46.
Preferred described matrix take silicon-dioxide as principal constituent and has the structure from fluorine-containing ether compound, and at least one party's end that described fluorine-containing ether compound has poly-(oxygen perfluorinated alkylidene) chain and described main chain on main chain has hydrolysable silanes base.
Preferred described fluorine-containing ether compound is the compound (A) represented by following formula (A),
RF1O(CF2CF2O)ACF2-(Q)B(-(CH2)D-SiLPR3-p)C(A)
Wherein, RF1For being inserted with the monovalence perfluor saturated hydrocarbyl of the carbon number 2��20 of etheric oxygen atom between the monovalence perfluor saturated hydrocarbyl of carbon number 1��20 or carbon atom-carbon atom, and it is not containing-OCF2The group of O-structure,
A is the integer of 1��200,
B is 0 or 1,
Q does not exist when b is 0, is that divalence or trivalent link base when b is 1,
C is 1 when Q does not exist or Q is bivalence linking base, is 2 when Q is trivalent link base,
D is the integer of 2��6,
L is hydrolization group,
R is hydrogen atom or monovalent hydrocarbon,
P is the integer of 1��3.
Preferred described hollow minute particle is hollow silica particles.
The manufacture method of the sheet glass having low-reflection film of the present invention is the manufacture method of the sheet glass with low-reflection film on the surface of sheet glass with the individual layer low-reflection film comprising matrix and hollow minute particle, possess: matrix precursor will be comprised, the coating solution of hollow minute particle and solvent is in the surface of sheet glass, carry out the operation burnt till, matrix precursor comprises silica precursor and fluorine-containing ether compound and/or its hydrolytic condensate, described fluorine-containing ether compound has poly-(oxygen perfluorinated alkylidene) chain on main chain, and at least one party's end of described main chain has hydrolysable silanes base, hollow minute particle in described coating fluid and silica precursor (SiO2Conversion) mass ratio (hollow minute particle/SiO2) it is 6/4��4/6, in coating fluid, the ratio of fluorine-containing ether compound is relative to hollow minute particle and silica precursor (SiO2Conversion) total amount (100 quality %) be 0.8��3.0 quality %.
In addition, above-mentioned " fluorine-containing ether compound and/or its hydrolytic condensate " at least one referring to the hydrolytic condensate being selected from fluorine-containing ether compound and fluorine-containing ether compound in this manual.
Preferred described fluorine-containing ether compound is the compound (A) represented by following formula (A),
RF1O(CF2CF2O)ACF2-(Q)B(-(CH2)D-SiLPR3-p)C(A)
RF1, a, b, Q, c, d, L, R have with p and aforementioned identical implication.
Preferred described silica precursor is the hydrolytic condensate of organoalkoxysilane.
Preferably in the modulating process with the coating fluid in the manufacture method of the sheet glass of low-reflection film of the present invention, after organoalkoxysilane is hydrolyzed, add compound (A), then add the dispersion liquid of hollow minute particle and obtain coating fluid.
Preferred described hollow minute particle is hollow silica particles.
Present invention also offers display unit, comprise framework, display unit, with the sheet glass with low-reflection film of the display surface being configured at described display unit, the described sheet glass with low-reflection film is the sheet glass with low-reflection film on the surface of sheet glass with the individual layer low-reflection film comprising matrix and hollow minute particle, the minimum reflectivity of the described low-reflection film within the scope of wavelength 300��1200nm is below 1.7%, the water contact angle on described low-reflection film surface is more than 97 ��, the oleic acid contact angle on described low-reflection film surface is more than 50 ��, the oleic acid on described low-reflection film surface tumbles angle below 25 ��.
In addition, present invention also offers the sheet glass with low-reflection film for display unit, the described sheet glass with low-reflection film is the sheet glass with low-reflection film on the surface of sheet glass with the individual layer low-reflection film comprising matrix and hollow minute particle, the minimum reflectivity of the described low-reflection film within the scope of wavelength 300��1200nm is below 1.7%, the water contact angle on described low-reflection film surface is more than 97 ��, the oleic acid contact angle on described low-reflection film surface is more than 50 ��, and the oleic acid on described low-reflection film surface tumbles angle below 25 ��.
That is, the display unit of the present invention is characterised in that, comprises framework, display unit and is configured at the described sheet glass with low-reflection film of the display surface of described display unit.
Present invention also offers the sheet glass for having low-reflection film described in display unit.
The sheet glass with low-reflection film of described display unit and for, in the sheet glass with low-reflection film that shows, described low-reflection film is all formed at the outside of outside, i.e. viewing person side or the operator side of display unit.
Invention effect
The present invention has, with the sheet glass of low-reflection film, the individual layer low-reflection film that reflectivity is enough low and greasy soils removability is good on the surface of sheet glass.
By the manufacture method of the sheet glass with low-reflection film of the present invention, it is possible to the surface being manufactured on sheet glass has the sheet glass with low-reflection film of the individual layer low-reflection film that reflectivity is enough low and greasy soils removability is good.
The display unit of the present invention possesses the sheet glass with the individual layer low-reflection film that reflectivity is enough low and greasy soils removability is good as the display unit of cover glass.
The simple explanation of accompanying drawing
Fig. 1 is the sheet glass with low-reflection film of display the present invention and the sectional view of an example of the sheet glass with low-reflection film for display unit.
Fig. 2 is example 37(embodiment) the scanning electron microscope photo of section of the sheet glass with low-reflection film.
Fig. 3 is the sectional view of an example of the display unit of display the present invention.
Embodiment
Fig. 1 is the sectional view of an example of the sheet glass with low-reflection film of display the present invention and the sheet glass with low-reflection film for display unit (sheet glass hereinafter referred to as with low-reflection film) of the present invention. With the sheet glass 10 of low-reflection film, there is sheet glass 12 and it is formed at the low-reflection film 14 on sheet glass 12 surface.
Fig. 3 is the sectional view of an example of the display unit 100 of display the present invention. Display unit 100 comprises the sheet glass 10(with low-reflection film for display unit hereinafter referred to as with the sheet glass 10 of low-reflection film), display unit 20 and framework 30. With the sheet glass 10 of low-reflection film, there is sheet glass 12 and it is formed at the low-reflection film 14 on sheet glass 12 surface. Low-reflection film 14 is formed on the face tossed about in the face relative with display unit of sheet glass.
In Fig. 1,3, become outside, i.e. viewing person side or the operator side of display unit with the top side of the low-reflection film 14 of the sheet glass 10 of low-reflection film.
The display unit of the present invention comprises mobile phone or carries the various display unit of the giant display or touch-screen etc. of the small-sized indicating meter of intelligent terminal etc., various televisors etc. Particularly, mobile phone, the chance carried intelligent terminal or touch-screen etc. and directly contacted by staff due to the display surface of display unit are frequent, and thus preferred concrete example as the display unit of the present invention with the sheet glass with low-reflection film of fingerprint removability excellence is enumerated.
As display unit, liquid crystal display component, plasma display parts or organic EL display unit etc. can be enumerated.
Framework is storage display unit 20 and the box like parts of the sheet glass 10 with low-reflection film, and material can enumerate resin or metal etc.
(sheet glass)
Sheet glass 12 can enumerate such as soda-lime glass, borosilicate glass, alumina silicate glass or non-alkali glass etc. , it is also possible to be the level and smooth sheet glass being shaped by float glass process etc., in addition or surface there is concavo-convex figured glass. In addition, the specific refractory power of sheet glass 12 is considered from the relation of the specific refractory power between low-reflection film, it is preferable to 1.45��1.60.
The surface of sheet glass 12 can be pre-formed the layer beyond the low-reflection film 14 of Alkali-barrier layer, undercoat etc.
(low-reflection film)
Low-reflection film 14 such as forms by being once coated with low-reflection film formation coating fluid described later, comprises the unitary film of matrix and hollow minute particle. But, low-reflection film 14 is by being repeatedly repeatedly coated with low-reflection film formation coating fluid and film forming is also harmless, and this film can regard the structure of the single layer structure playing the function as low-reflection film or substantially individual layer as.
As matrix, the angle of lower from specific refractory power, can to obtain antiradar reflectivity, chemically excellent in stability and sheet glass 12 excellent adhesion is considered, it is preferable that take silicon-dioxide as principal constituent, again containing a small amount of composition with the structure from fluorine-containing ether compound. Except having except the composition of the structure of fluorine-containing ether compound in matrix, it is preferable that be substantially made up of silicon-dioxide. So-called is that principal constituent refers to that the ratio of silicon-dioxide accounts for more than 90 quality % in matrix (100 quality %) taking silicon-dioxide, is substantially made up of silicon-dioxide and refers to except being only made up of silicon-dioxide except the structure of compound described later (A) and inevitable impurity.
In addition, consider from the angle of greasy soils removability excellence, matrix preferably has the structure from fluorine-containing ether compound described later, and at least one party's end that described fluorine-containing ether compound has poly-(oxygen perfluorinated alkylidene) chain and aforementioned backbone on main chain has hydrolysable silanes base.
As matrix, the burned material etc. of at least one matrix precursor being selected from following matrix precursor (a) and (b) and (c) can be enumerated, consider from the angle of greasy soils removability excellence, it will be preferred that the burned material of matrix precursor (a).
A () comprises silica precursor described later and the matrix precursor of fluorine-containing ether compound described later.
B () comprises the matrix precursor of the hydrolytic condensate between silica precursor described later, fluorine-containing ether compound described later and fluorine-containing ether compound.
C () comprises the hydrolytic condensate between silica precursor described later, fluorine-containing ether compound described later and the matrix precursor of the hydrolytic condensate between silica precursor (organoalkoxysilane) and fluorine-containing ether compound.
As the sheating material of hollow minute particle, Al can be enumerated2O3, SiO2, SnO2, TiO2, ZrO2, ZnO, CeO2, containing the SnO of SbX(ATO), containing the In of Sn2O3(ITO), RuO2Deng. Can be used alone one wherein, it is possible to and with two or more.
In addition, as the shape of hollow minute particle, shape spherical, oval, needle-like, tabular, bar-shaped, circular cone shape, cylinder shape, cubic, rectangular-shaped, diamond-like, starlike, irregular shape etc. can be enumerated.
In addition, hollow minute particle can each particulate independence state exist, it is also possible to each particulate connects to chain shape, or each microparticle agglutination.
As hollow minute particle, the angle of low from the specific refractory power of low-reflection film 14, can to obtain antiradar reflectivity, chemically excellent in stability and sheet glass 12 excellent adhesion is considered, it will be preferred that hollow silica particles.
The average primary particle diameter of hollow silica particles is preferably 5��150nm, is more preferably 50��100nm. If the average primary particle diameter of hollow silica particles is at more than 5nm, then the reflectivity of low-reflection film 14 becomes enough low. If the average primary particle diameter of hollow silica particles is at below 150nm, then the haze value of low-reflection film 14 can reduce.
Average primary particle diameter by selecting 100 particulates at random from electron micrograph, measure the particle diameter of each particulate, the mean value of the particle diameter of a particulate of getting 100 and obtain.
The minimum reflectivity of the low-reflection film 14 within the scope of wavelength 300��1200nm below 1.7%, preferably 0.2��1.7%, more preferably 0.8��1.1%, further preferably 0.9��1.0%. If the minimum reflectivity of low-reflection film 14 is below 1.7%, then fully meet the required antiradar reflectivity such as various indicating meter, window glass for automobile or touch-screen with the sheet glass 10 of low-reflection film. If the minimum reflectivity of low-reflection film 14 is greater than 1.7%, then there is the situation of low reflection characteristic deficiency.
The water contact angle on low-reflection film 14 surface more than 97 ��, preferably 95 �㡫121 ��, more preferably 97 �㡫109 ��, further preferably 97 �㡫99 ��.
The oleic acid contact angle on low-reflection film 14 surface more than 50 ��, preferably 50 �㡫90 ��, more preferably 52 �㡫87 ��, particularly preferably 55 �㡫85 ��.
The oleic acid on low-reflection film 14 surface tumble angle below 25 ��, preferably 5 �㡫25 ��, more preferably 5 �㡫20 ��, further preferably 6 �㡫10 ��.
If the water contact angle on low-reflection film 14 surface, oleic acid contact angle and oleic acid tumble angle meets aforementioned range simultaneously, then the greasy soils removability on low-reflection film 14 surface becomes good.
The ratio of the fluorine element on described low-reflection film 14 surface measured by X-ray photoelectron spectroscopy is preferably 3��20 atom %, is more preferably 5��18 atom %, more preferably 5��16 atom %. The ratio of the fluorine element on low-reflection film 14 surface represent from the fluorochemicalss such as compound described later (A) structure with which kind of degree be present in low-reflection film 14 surface and near. If the ratio of the fluorine element on low-reflection film 14 surface is at 3 more than atom %, then greasy soils removability improves further. If the ratio of the fluorine element on low-reflection film 14 surface is at 20 below atom %, then preferred because maintaining low reflectivity when not affecting the optical design of film. In addition, X-ray photoelectron spectroscopy owing to being observe the method for photoelectron escaped because of the irradiation of X-ray from specimen surface, therefore analytical results be the photoelectron that can observe the degree of depth of escaping, more specifically from the outermost surface of the air side of low-reflection film to the analysis information of the outermost surface of about a few nm��tens nm degree of depth.
The arithmetic average roughness (Ra) on low-reflection film 14 surface measured by scanning type probe microscope device is preferably 3.0��5.0nm, is more preferably 3.0��4.5nm, more preferably 3.0��4.0nm. If the arithmetic average roughness (Ra) on low-reflection film 14 surface is at more than 3.0nm, then demonstrating and formed very trickle concavo-convex, water-and oil-repellency easily improves. If the arithmetic average roughness (Ra) on low-reflection film 14 surface is at below 5.0nm, then greasy soils removability improves further.
The specific refractory power of low-reflection film 14 is preferably 1.20��1.46, is more preferably 1.20��1.40, more preferably 1.20��1.35. If the specific refractory power of low-reflection film 14 is more than 1.20, then the porosity of low-reflection film 14 can not become too high, and weather resistance rises. If the specific refractory power of low-reflection film 14 is below 1.46, then the reflectivity of low-reflection film 14 fully reduces.
The specific refractory power n of low-reflection film 14 is calculated via following formula (1) by the specific refractory power ns of minimum reflectivity (i.e. so-called bottom reflection rate (�� �� system the reflectivity)) Rmin within the scope of the wavelength 30��1200nm of spectrophotometric determination and sheet glass 12 by the individual layer low-reflection film 14 being formed at sheet glass 12 surface.
Rmin=(n-ns)2/ (n+ns)2(1).
The thickness of low-reflection film 14 is preferably 80��100nm, is more preferably 85��95nm. If the thickness of low-reflection film 14 is at more than 80nm, then present the weather resistance of low-reflection film 14. If the thickness of low-reflection film 14 is at below 100nm, though then changing according to the specific refractory power of film used, but preferred because presenting the low reflectivity as unitary film.
The thickness of low-reflection film 14 is measured by the image obtained with the section of scanning electron microscope observation low-reflection film 14.
(manufacture method of sheet glass with low-reflection film)
The present invention with low-reflection film sheet glass 10 by such as by for the formation of low-reflection film 14 coating solution in the surface of sheet glass 12, according to needed for carry out preheating, manufacture finally by burning till.
Coating fluid comprises matrix precursor, hollow minute particle and solvent.
Coating fluid can comprise the tensio-active agent for improving smooth property or the metallic compound etc. for the weather resistance that improves low-reflection film 14.
Matrix precursor comprises silica precursor and fluorine-containing ether compound and/or its hydrolytic condensate, and at least one party's end that described fluorine-containing ether compound has poly-(oxygen perfluorinated alkylidene) chain and described main chain on main chain has hydrolysable silanes base.
The hydrolytic condensate of described fluorine-containing ether compound can be the hydrolytic condensate between fluorine-containing ether compound, it is also possible to be the hydrolytic condensate between the organoalkoxysilane as silica precursor and fluorine-containing ether compound.
As matrix precursor, specifically can enumerate and be selected from following matrix precursor (a) and (b) and at least one matrix precursor of (c), consider from the angle of the greasy soils removability excellence of low-reflection film 14, it is more preferable to be matrix precursor (a).
A () comprises silica precursor and the matrix precursor of fluorine-containing ether compound.
B () comprises the matrix precursor of the hydrolytic condensate of silica precursor, fluorine-containing ether compound and compound (A).
C () comprises the hydrolytic condensate between silica precursor, fluorine-containing ether compound and the matrix precursor of the hydrolytic condensate between silica precursor (organoalkoxysilane) and fluorine-containing ether compound.
As silica precursor, the hydrolytic condensate (sol-gel silica) or silazane etc. of organoalkoxysilane, organoalkoxysilane can be enumerated, consider from the angle of each characteristic of low-reflection film 14, it will be preferred that the hydrolytic condensate of organoalkoxysilane.
As organoalkoxysilane, tetraalkoxysilane (tetramethoxy-silicane can be enumerated, tetraethoxysilane, tetrapropoxysilane or four butoxy silanes etc.), there is the organoalkoxysilane (perfluor many ether triethoxyl silane etc.) of perfluor many ether base, there is the organoalkoxysilane (perfluoro-ethyl triethoxyl silane etc.) of perfluoroalkyl, there is the organoalkoxysilane (vinyltrimethoxy silane or vinyltriethoxysilane etc.) of vinyl, there is the organoalkoxysilane (2-(3 of epoxy group(ing), the own base of 4-oxirane ring) ethyl trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyldiethoxysilane or 3-glycidoxy propyl-triethoxysilicane etc.), or there is the organoalkoxysilane (3-acryloxy propyl trimethoxy silicane etc.) of acryloxy.
The hydrolysis of organoalkoxysilane is under the occasion of tetraalkoxysilane, and the water of more than 4 times moles and the acid or alkali as catalyzer with the use of organoalkoxysilane carry out. As acid, mineral acid (such as nitric acid, sulfuric acid or hydrochloric acid etc.) or organic acid (such as formic acid, oxalic acid, Monochloro Acetic Acid, dichloro acetic acid or trichoroacetic acid(TCA) etc.) can be enumerated. As alkali, ammonia, sodium hydroxide or potassium hydroxide etc. can be enumerated. As catalyzer, consider from the angle of the long-term keeping quality of the hydrolytic condensate of organoalkoxysilane, it will be preferred that acid. As catalyzer used in the hydrolysis of organoalkoxysilane, it will be preferred that do not hinder the catalyzer of the dispersion of hollow minute particle.
Fluorine-containing ether compound can have hydrolysable silanes base at side's end of main chain, it is also possible to two side's ends at main chain all have hydrolysable silanes base. Consider from fully giving low reflection layer with the angle of rub, it is preferable that only side's end at main chain has hydrolysable silanes base.
So-called low reflection layer, refers to the outermost surface part of the film that layer, i.e. fingerprint or the spot of the outermost surface being formed at film directly contact.
Fluorine-containing ether compound can be single compound, it is also possible to be the different mixtures of more than two kinds such as poly-(oxygen perfluorinated alkylidene) chain, terminal group or link base.
The number-average molecular weight of fluorine-containing ether compound is preferably 500��10000, is more preferably 800��8000. If number-average molecular weight is in aforementioned range, then rub is excellent. Considering from the angle of the consistency between other composition of formation matrix precursor, the number-average molecular weight of aforesaid compound is particularly preferably 800��2000.
It has been generally acknowledged that, the number-average molecular weight of fluorine-containing ether compound is more little, and the chemical bond between base material becomes more firm. Its reason thinks the cause that the number of the hydrolysable silanes base that corresponding per unit molecular weight exists becomes many. But the present inventor etc. confirm, if number-average molecular weight is less than the lower value of aforementioned range, then rub easily declines. In addition, if number-average molecular weight exceedes the higher limit of above-mentioned scope, then rub decline. Its reason is thought the reduced number of the hydrolysable silanes base due to corresponding per unit molecular weight existence and is caused affecting the cause increased.
Fluorine-containing ether compound has poly-(oxygen perfluorinated alkylidene) chain, and therefore the content of fluorine atom is many. So, fluorine-containing ether compound can form the low reflection layer of the water-and oil-repellency height at initial stage, rub or fingerprint spot removability excellence.
Hydrolysable silanes base ((-SiL in fluorine-containing ether compoundMR3-m) forming silanol group (Si-OH) through hydrolysis reaction, the hydroxyl (base material-OH) that aforementioned silane alcohol radical forms Si-O-Si key or aforementioned silane alcohol radical and substrate surface through intermolecular reaction forms chemical bond (base material-O-Si) through dehydration condensation. That is, the low reflection layer in the present invention comprises this compound with part or all of hydrolysable silanes base of this compound through the state of hydrolysis reaction.
As fluorine-containing ether compound, such as, can enumerate compound (A).
The compound of compound (A) represented by following formula (A).
RF1O(CF2CF2O)ACF2-(Q)B(-(CH2)D-SiLPR3-p)C(A)
RF1For being inserted with the monovalence perfluor saturated hydrocarbyl of the carbon number 2��20 of etheric oxygen atom between the monovalence perfluor saturated hydrocarbyl of carbon number 1��20 or carbon atom-carbon atom, and it is not containing-OCF2The group of O-structure.
A is integer, the preferably integer of 2��100, the integer of the integer being more preferably 3��50, more preferably 5��25 of 1��200.
B is 0 or 1, is preferably 1.
Q does not exist when b is 0, is that divalence or trivalent link base when b is 1.
C is 1 when Q does not exist or Q is bivalence linking base, is 2 when Q is trivalent link base.
D is the integer of 2��6.
R is hydrogen atom or monovalent hydrocarbon.
L is hydrolization group. So-called hydrolization group is the group that can form Si-OH base through the hydrolysis of Si-L base.
As L, alkoxyl group, acyloxy, ketoxime base, alkene oxygen base, amino, aminooxy, amide group, isocyanate group or halogen atom etc. can be enumerated, consider from the angle of the stability of compound (A) and the easiness of hydrolysis, it will be preferred that alkoxyl group, isocyanate group and halogen atom (particularly chlorine atom). As alkoxyl group, it will be preferred that the alkoxyl group of carbon number 1��3, it is more preferable to be methoxy or ethoxy. When in fluorochemicals, L exists more than 2, the group that L can be identical can also be different group, for identical group is preferred from the angle easily obtained.
P is the integer of 1��3. If p is more than 1, then the structure from compound (A) can be made firmly to be incorporated into matrix by the condensation between Si-OH base. P is preferably 2 or 3, is particularly preferably 3.
As compound (A), consider from the angle of greasy soils removability and the synthesis easiness of compound (A), it will be preferred that following compound (A-1) or compound (A-2).
CF3O(CF2CF2O)A1CF2C(O) NH-(CH2)3-Si(OCH3)3(A-1).
CF3O(CF2CF2O)A2CF2CH2O(CH2)3Si(OCH3)3(A-2).
Wherein, a1 and a2 is the integer of 5��25.
There is not-OCF in compound (A)2O-structure, even if therefore in the presence of acid catalyst and under the high temperature conditions, also can form the low-reflection film 14 of deterioration patience excellence.
In addition, (the CF of compound (A)2CF2O) a structure there is not the CF that transport properties of molecules is reduced3The alkylene oxide structure of base. Therefore, the transport properties of molecules of compound (A) itself improves, and the low-reflection film 14 formed by the matrix precursor comprising compound (A) becomes the film of greasy soils removability excellence.
Hollow minute particle in coating fluid and silica precursor (SiO2Conversion) mass ratio (hollow minute particle/SiO2) it is preferably 6/4��4/6. If the ratio of hollow minute particle is less than 6/4, then the arithmetic average roughness (Ra) on low-reflection film 14 surface diminishes, and the greasy soils removability of low-reflection film 14 rises. If the ratio of hollow minute particle is greater than 4/6, then the specific refractory power of low-reflection film 14 becomes low, and the reflectivity of low-reflection film 14 fully reduces.
In coating fluid, the ratio of fluorine-containing ether compound is relative to hollow minute particle and silica precursor (SiO2Conversion) total amount (100 quality %) be preferably 0.8��3.0 quality %, be more preferably 1.0��1.8 quality %. If the ratio of fluorine-containing ether compound is at more than 0.8 quality %, then greasy soils removability rises further. If the ratio of fluorine-containing ether compound is at below 2.0 quality %, then can not occur to concentrate, because of fluorine-containing ether compound, the local being present in film surface and cause the situations such as mist degree rising, thus preferably.
As solvent, the dispersion medium etc. of the solvent of the solution of matrix precursor, the dispersion liquid of hollow minute particle can be enumerated.
As the solvent of solution of the hydrolytic condensate of organoalkoxysilane, it will be preferred that the mixed solvent of water and alcohol class (such as methyl alcohol, ethanol, Virahol, butanols or Pyranton etc.).
As the solvent of the solution of fluorine-containing ether compound, it will be preferred that organic solvent. Organic solvent can be fluorine system organic solvent, it is also possible to be non-fluorine system organic solvent, it is also possible to be the solvent comprising both. As aforementioned solvents, methyl alcohol or ethanol etc. can be enumerated.
As the dispersion medium of the dispersion liquid of hollow minute particle, water, alcohol class, ketone class, ether class, cellosolve class, ester class, glycol ethers, nitrogenous compound or sulfocompound etc. can be enumerated.
As the modulator approach of coating fluid, the method of following method (��) to (��) can be enumerated, when by coating solution in sheet glass 12 surface, fluorine-containing ether compound floats the surface of film, burn till and concentrated, from the structure of fluorine-containing ether compound, the surface being present in low-reflection film 14 afterwards, consider from the angle having given play to excellent greasy soils removability, it will be preferred that method (��). In addition, considering from the angle of the aggegation suppressing hollow minute particle, the dispersion liquid of hollow minute particle preferably adds after by the solution dilution of matrix precursor.
(��) method of the dispersion liquid of hollow minute particle is carried out diluting, then adding after organoalkoxysilane in the solution and fluorine-containing ether compound hydrolysis according to required solvent.
(��) in the solution organoalkoxysilane hydrolysis after (preferably from hydrolysis start after the time of more than 2 hours) add the solution of fluorine-containing ether compound, carry out diluting, then adding the method for the dispersion liquid of hollow minute particle according to required solvent.
(��) organoalkoxysilane in the solution carries out diluting, then adding the solution of fluorine-containing ether compound, add the method for the dispersion liquid of hollow minute particle again with solvent after being hydrolyzed.
As coating process, known wet coating method (such as spin-coating method, spraying method, dip coating, mould are coated with method, curtain painting method, silk screen printing coating method, ink jet method, flow coat method, intaglio printing coating method, stick coating method, offset printing coating method, slot coated method or rolling method etc.) etc. can be enumerated.
Coating temperature is preferably room temperature��200 DEG C, is more preferably room temperature��150 DEG C.
Firing temperature preferably more than 30 DEG C, be more preferably 100��180 DEG C, suitably can determine according to the material of sheet glass, particulate or matrix.
Firing time preferably more than 3 minutes, be more preferably 10 minutes��60 minutes, suitably can determine according to the material of sheet glass, particulate or matrix.
The present invention with the sheet glass of low-reflection film be sheet glass surface there is the sheet glass with low-reflection film of the individual layer low-reflection film comprising matrix and hollow minute particle, it is said hollow silicon dioxide microparticle that preferred aforementioned matrix has structure and the said hollow particulate from aforementioned fluorine-containing ether compound, it is more preferable to aforementioned fluorine-containing ether compound is the compound (A) represented by following formula (A).
The sheet glass with low-reflection film of the present invention is by manufacturing the coating solution comprising matrix precursor, hollow minute particle and solvent in the surface of sheet glass.
That is, the present invention has low-reflection film on the surface with the sheet glass of low-reflection film, and aforementioned low-reflection film comprises matrix precursor and hollow minute particle. aforementioned low-reflection film is preferably by comprising matrix precursor, the coating fluid of hollow silica particles and solvent is formed, wherein matrix precursor comprises silica precursor and fluorine-containing ether compound and/or its hydrolytic condensate, described coating fluid more preferably comprises matrix precursor, hollow silica particles and solvent, wherein matrix precursor comprises the hydrolytic condensate between the compound (A) represented by tetraalkoxysilane and following formula (A), preferably comprise matrix precursor further, hollow silica particles and solvent, wherein matrix precursor comprises the hydrolytic condensate between the compound (A) represented by tetraethoxysilane and following formula (A).
RF1O(CF2CF2O)ACF2-(Q)B(-(CH2)D-SiLPR3-p)C(A).
RF1, a, b, Q, c, d, L, R have with p and aforementioned identical implication.
(action effect)
The present invention's described above is the sheet glass with low-reflection film on the surface of sheet glass with the individual layer low-reflection film comprising matrix and hollow minute particle with the sheet glass of low-reflection film, the minimum reflectivity of the aforementioned low-reflection film within the scope of wavelength 300��1200nm is below 1.7%, the water contact angle on aforementioned low-reflection film surface is more than 97 ��, the oleic acid contact angle on aforementioned low-reflection film surface is more than 50 ��, the oleic acid on aforementioned low-reflection film surface tumbles angle below 25 ��, therefore, the reflectivity of low-reflection film is enough low and greasy soils removability is good.
The present invention described above possesses the surface of coating solution in sheet glass comprising matrix precursor, hollow minute particle and solvent with the manufacture method of sheet glass of low-reflection film, carries out the operation burnt till, described matrix precursor comprises silica precursor and fluorine-containing ether compound and/or its hydrolytic condensate, at least one party's end that described fluorine-containing ether compound has poly-(oxygen perfluorinated alkylidene) chain and described main chain on main chain has hydrolysable silanes base, hollow minute particle in coating fluid and silica precursor (SiO2Conversion) mass ratio (hollow minute particle/SiO2) it is 6/4��4/6, in coating fluid, the ratio of fluorine-containing ether compound is relative to hollow minute particle and silica precursor (SiO2Conversion) total amount (100 quality %) be 0.8��3.0 quality %, the surface that therefore can manufacture sheet glass has the sheet glass with low-reflection film of the individual layer low-reflection film that reflectivity is enough low and greasy soils removability is good of low-reflection film.
The surface that the display unit of the present invention described above comprises sheet glass has the sheet glass with low-reflection film of the individual layer low-reflection film comprising matrix and hollow minute particle. And, in the aforementioned sheet glass with low-reflection film, the minimum reflectivity of the aforementioned low-reflection film within the scope of wavelength 300��1200nm is below 1.7%, the water contact angle on aforementioned low-reflection film surface is more than 97 ��, the oleic acid contact angle on aforementioned low-reflection film surface is more than 50 ��, the oleic acid on aforementioned low-reflection film surface tumbles angle below 25 ��, and therefore, the reflectivity of low-reflection film is enough low and greasy soils removability is good.
Embodiment
The present invention will be described in more detail by the following examples.
Example 15��18,21��23,26��28,31��34,37��42,45��50,53��58 and 61��66 is embodiment, and example 1��14,19,20,24,25,29,30,35,36,43,44,51,52,59 and 60 is comparative example.
(visual sense reflectivity)
The reflectivity of low-reflection film uses spectrophotometer (Hitachi makes made, model: U-4100) to measure. Visual sense reflectivity is the reflectivity obtained through equalization after the reflectivity of wavelength 380��780nm is multiplied by weighting function.
(minimum reflectivity)
Use spectrophotometer (Hitachi makes made, model: U-4100) to measure the reflectivity within the scope of wavelength 300��1200nm, obtain the minimum value (minimum reflectivity) of reflectivity.
(mist degree)
Mist degree determinator (Bi Ke-Gartner company (BYK-Gardner society) system, Haze-guardPlus) is used to measure with the mist degree of the sheet glass of low-reflection film.
(water contact angle)
The surface of low-reflection film is placed the distilled water of three places about 48 �� L, it may also be useful to contact angle meter (consonance interface science Co., Ltd. (with interface science society) system, FAMAS) measures respective water contact angle, obtains the mean value of 3 values.
(oleic acid contact angle)
The surface of low-reflection film is placed the oleic acid of three places about 48 �� L, it may also be useful to contact angle meter (consonance interface science Co., Ltd. (with interface science society) system, FACESLIDINGANGLEMETER) measures respective oleic acid contact angle, obtains the mean value of 3 values.
(oleic acid tumbles angle)
Sheet glass with low-reflection film is kept level, drip in the surface of low-reflection film 48 �� L oleic acid after, slowly tilt the sheet glass with low-reflection film, measure oleic acid start when tumbling with the sheet glass of low-reflection film and the angle (tumbling angle) of horizontal plane. As measurement result, " cannot measure " represents that oleic acid launches on substrate, even if tilting the state of the movement etc. that also cannot observe oleic acid with the sheet glass of low-reflection film.
(ratio of fluorine element)
For 3 pieces of example 11,23 and 35 sheet glass with low-reflection film, it may also be useful to x-ray photoelectron spectroscopy device (A Er Wacker process Co., Ltd. (�� Le �� �� Network Off �� �� society) system, QuanteraSXM) obtains the ratio of the fluorine element on low-reflection film surface. The ratio of fluorine element making low-reflection film surfaces from the measurement results of 3 is relative to the calibration curve of the ratio of the compound (A) coating fluid. For the sheet glass with low-reflection film of other example except example 11,23 and 35, it may also be useful to the ratio of the compound (A) of calibration curve in coating fluid obtains the ratio of the fluorine element on low-reflection film surface.
(arithmetic average roughness)
The arithmetic average roughness (Ra) on low-reflection film surface uses scanning type probe microscope device (SII nanotechnology Co., Ltd. (SII Na �� �� Network �� �� �� society) system, SPA400DFM) to measure.
(specific refractory power)
The specific refractory power n of low-reflection film is calculated by following formula (1) by the specific refractory power ns of the minimum reflectivity Rmin within the scope of the wavelength 300��1200nm to individual layer low-reflection film spectrophotometric determination and sheet glass.
Rmin=(n-ns)2/ (n+ns)2(1).
(greasy soils tack)
Use permanent pen (zebra company (�� Block �� society) system, mark's (registered trademark)) to draw straight line on the surface of low-reflection film, evaluate according to following standard.
A: line all becomes water droplet shape, the state cannot clear write completely.
B a: part for line becomes water droplet shape, as the state that line can be recognized.
C: can be drawn as line, can be recognized as line clearly.
(greasy soils removability)
After have rated greasy soils tack, with the oily ink on wiping (kimwipe) paper wiping low-reflection film surface, evaluate according to following standard.
A: only wipe and namely wipe oily ink completely three times.
B: substantially wipe during wiping 10 times, but slightly remain oiliness ink marks.
C: during wiping 30 times, oily ink color slightly becomes shallow, but substantially cannot wipe.
D: during wiping 100 times, oily ink color slightly becomes shallow, but substantially cannot wipe.
E: even if wiping 100 times, oily ink color is also completely unchanged.
(sheet glass)
As sheet glass, prepare soda-lime glass (Asahi Glass Co., Ltd (Xu Xiaozi society) system, size: 100mm �� 100mm, thickness 3.2mm, specific refractory power: 1.52, transmission of visible light: 90.4%).
(compound (A))
As compound (A), prepare compound (A-1).
Compound (A-1) adopts the method described in embodiment 1 and 2 of No. 2009/008380th, International Publication to manufacture.
(organoalkoxysilane)
As organoalkoxysilane, prepare solution (pure chemistry Co., Ltd. (positive chemistry society) system, the SiO of tetraethoxysilane (hereinafter referred to as TEOS)2Conversion solid component concentration: 5 quality %, Virahol: 30 quality %, 2-butanols: 25 quality %, ethanol: 8 quality %, Pyranton: 15 quality %, methyl alcohol: 17 quality %).
(hollow minute particle)
As hollow minute particle, prepare following material.
The dispersion liquid of hollow silica particles (C-1): Asahi Glass Co., Ltd's system, hollow-particle colloidal sol, SiO2Conversion solid component concentration: 20 quality %, average primary particle diameter: 10nm, water: 40 quality %, alcohol: 40 quality %.
The dispersion liquid of hollow silica particles (C-2): RiHui catalyst synthesis Co., Ltd's (day catalyst chemical conversion society) system, hollow-particle colloidal sol, SiO2 convert solid component concentration: 20 quality %, average primary particle diameter: 20nm, alcohol: 80 quality %.
Example 1
In the TEOS solution of 10g, add the 8mol/L aqueous nitric acid of 0.02g, stir 2 hours, obtain the solution of the hydrolytic condensate of TEOS.
In the solution of the hydrolytic condensate of TEOS, add the solution of the compound (A-1) of 0.005g, stir after 15 minutes, add the mixed solvent (Virahol: 30 quality %, 2-butanols: 25 quality %, ethanol: 8 quality %, Pyranton: 15 quality %, methyl alcohol: 17 quality %) of 12g, stir 120 minutes, obtain the solution of matrix precursor.
In the solution of matrix precursor, add the dispersion liquid of the hollow silica particles (C-1) of 6g, stir 15 minutes, obtain coating fluid. The composition of coating fluid is shown in table 1.
Coating fluid is revolved painting (180rpm, 60 minutes) and after the surface of sheet glass, at 150 DEG C, burns till 30 minutes, obtain the sheet glass with low-reflection film. It is shown in table 2 with the evaluation result of the sheet glass of low-reflection film.
Example 2
Except the rotating speed revolving painting is changed to 250rpm by 180rpm, and example 1 obtains the sheet glass with low-reflection film equally. The composition of coating fluid is shown in table 1, is shown in table 1 with the evaluation result of the sheet glass of low-reflection film.
Example 3��12
Except the composition of coating fluid is changed to the composition shown in table 1, and example 1 and example 2 obtain the sheet glass with low-reflection film equally. Evaluate the aforementioned sheet glass with low-reflection film. The results are shown in table 2. Table 1
Table 2
Example 13��23
Except the ratio of compound (A-1) is changed to the ratio shown in table 3, and example 1��12 obtains the sheet glass with low-reflection film equally. Evaluate the aforementioned sheet glass with low-reflection film. The results are shown in table 4.
Table 3
Table 4
Example 24��34
Except the ratio of compound (A-1) is changed to the ratio shown in table 5, and example 1��12 obtains the sheet glass with low-reflection film equally. Evaluate the aforementioned sheet glass with low-reflection film. The results are shown in table 6.
Table 5
Table 6
Example 35��42
Except the composition of coating fluid being changed to the composition shown in table 7, the interpolation of compound (A-1) be changed to opportunity TEOS be hydrolyzed before except, and example 1��12 obtains the sheet glass with low-reflection film equally. Evaluate the aforementioned sheet glass with low-reflection film. The results are shown in table 8.
Example 43��50
Except the interpolation of compound (A-1) being changed to opportunity TEOS and is hydrolyzed after 1 hour, and example 35��42 obtains the sheet glass with low-reflection film equally. Evaluate the aforementioned sheet glass with low-reflection film. The results are shown in table 8.
Table 7
Table 8
Example 51��58
Except the interpolation of compound (A-1) being changed to opportunity TEOS and is hydrolyzed after 2 hours, and example 35��42 obtains the sheet glass with low-reflection film equally. Evaluate the aforementioned sheet glass with low-reflection film. The results are shown in table 10.
Example 59��66
Except after after the interpolation of compound (A-1) being changed to opportunity TEOS and being hydrolyzed 2 hours and with solvent cut, and example 35��42 obtains the sheet glass with low-reflection film equally. Evaluate the aforementioned sheet glass with low-reflection film. The results are shown in table 10.
Table 9
Table 10
The scanning electron microscope photo of the section of the sheet glass having low-reflection film of example 37 is shown in Fig. 2. Shown in Fig. 2 is the SEM picture of multiplying power of cut off the film profile direction obtained with the sheet glass of low-reflection film with focused ion beam 100000 times. The about 100nm of the thickness of low-reflection film, is made up of hollow-particle and matrix components (silicon-dioxide and fluorine cpd). Film confirms be the part in free hole be hollow-particle cut-off after can see the position in empty hole of hollow-particle inside.
Industry utilizes possibility
The sheet glass with low-reflection film of the present invention and by obtained can be used as the sheet glass for various indicating meter, window glass for automobile or touch-screen etc. with the sheet glass of low-reflection film and use of the manufacture method of the present invention.
The display unit of the present invention can be used for various televisor, touch-screen, mobile phone or carries intelligent terminal etc.
In addition, quote here the Japanese patent application laid filed an application in Japan on April 1st, 2011 be willing to the Japanese patent application laid filed an application in Japan on April 1st, No. 2011-081719 1 be willing to No. 2011-081720 and the Japanese patent application laid filed an application in Japan on April 1st, 2011 be willing to No. 2011-081833 specification sheets, claim book, accompanying drawing and summary whole contents as the announcement of the present invention.
The explanation of symbol
10 have the sheet glass of low-reflection film
12 sheet glass
14 low-reflection films
100 display unit
20 display units
30 frameworks
Claims (14)
1., with the sheet glass of low-reflection film, it is the sheet glass with low-reflection film on the surface of sheet glass with the individual layer low-reflection film comprising matrix and hollow minute particle, wherein,
The minimum reflectivity of the described low-reflection film within the scope of wavelength 300��1200nm below 1.7%,
The water contact angle on described low-reflection film surface more than 97 ��,
The oleic acid contact angle on described low-reflection film surface more than 50 ��,
The oleic acid on described low-reflection film surface tumbles angle below 25 ��, and
The described individual layer low-reflection film comprising matrix and hollow minute particle is formed at the outermost layer of at least one side of described sheet glass.
2. the sheet glass with low-reflection film as claimed in claim 1, it is characterised in that, the ratio of the fluorine element on the described low-reflection film surface measured by X-ray photoelectron spectroscopy is 3��20 atom %.
3. the sheet glass with low-reflection film as claimed in claim 1, it is characterised in that, the arithmetic average roughness (Ra) on the described low-reflection film surface measured by scanning type probe microscope device is 3.0��5.0nm.
4. the sheet glass with low-reflection film as claimed in claim 1, it is characterised in that, the specific refractory power of described low-reflection film is 1.20��1.46.
5. the sheet glass with low-reflection film as claimed in claim 1, it is characterized in that, described matrix take silicon-dioxide as principal constituent and has the structure from fluorine-containing ether compound, and at least one party's end that described fluorine-containing ether compound has poly-(oxygen perfluorinated alkylidene) chain and described main chain on main chain has hydrolysable silanes base.
6. the sheet glass with low-reflection film as claimed in claim 5, it is characterised in that, described fluorine-containing ether compound is the compound (A) represented by following formula (A),
RF1O(CF2CF2O)aCF2-(Q)b(-(CH2)d-SiLpR3-p)c������(A)
Wherein, RF1For being inserted with the monovalence perfluor saturated hydrocarbyl of the carbon number 2��20 of etheric oxygen atom between the monovalence perfluor saturated hydrocarbyl of carbon number 1��20 or carbon atom-carbon atom, and it is not containing-OCF2The group of O-structure,
A is the integer of 1��200,
B is 0 or 1,
Q does not exist when b is 0, is that divalence or trivalent link base when b is 1,
C is 1 when Q does not exist or Q is bivalence linking base, is 2 when Q is trivalent link base,
D is the integer of 2��6,
L is hydrolization group,
R is hydrogen atom or monovalent hydrocarbon,
P is the integer of 1��3.
7. the sheet glass with low-reflection film as claimed in claim 1, it is characterised in that, described hollow minute particle is hollow silica particles.
8. the sheet glass with low-reflection film as claimed in claim 1, it is characterised in that, for display unit.
9. has the manufacture method of the sheet glass of low-reflection film, it is there is on the surface of sheet glass the individual layer low-reflection film comprising matrix and hollow minute particle and this low-reflection film is formed at the manufacture method of the outermost sheet glass with low-reflection film of at least one side of described sheet glass, possesses:
By comprising the surface of coating solution in sheet glass of matrix precursor, hollow minute particle and solvent, carry out the operation burnt till,
Described matrix precursor comprises silica precursor and fluorine-containing ether compound and/or its hydrolytic condensate, and at least one party's end that described fluorine-containing ether compound has poly-(oxygen perfluorinated alkylidene) chain and described main chain on main chain has hydrolysable silanes base,
Hollow minute particle in described coating fluid and the SiO of silica precursor2The mass ratio of conversion quality and hollow minute particle/SiO2It is 6/4��4/6,
In coating fluid, the ratio of fluorine-containing ether compound is relative to the SiO of hollow minute particle and silica precursor2The total amount 100 quality % of conversion quality is 0.8��3.0 quality %.
10. the manufacture method of the sheet glass with low-reflection film as claimed in claim 9, it is characterised in that, described fluorine-containing ether compound is the compound (A) represented by following formula (A),
RF1O(CF2CF2O)aCF2-(Q)b(-(CH2)d-SiLpR3-p)c������(A)
Wherein, RF1For being inserted with the monovalence perfluor saturated hydrocarbyl of the carbon number 2��20 of etheric oxygen atom between the monovalence perfluor saturated hydrocarbyl of carbon number 1��20 or carbon atom-carbon atom, and it is not containing-OCF2The group of O-structure,
A is the integer of 1��200,
B is 0 or 1,
Q does not exist when b is 0, is that divalence or trivalent link base when b is 1,
C is 1 when Q does not exist or Q is bivalence linking base, is 2 when Q is trivalent link base,
D is the integer of 2��6,
L is hydrolization group,
R is hydrogen atom or monovalent hydrocarbon,
P is the integer of 1��3.
The manufacture method of 11. sheet glass with low-reflection film as described in claim 9 or 10, it is characterised in that, described silica precursor is the hydrolytic condensate of organoalkoxysilane.
12. as claimed in claim 11 with the manufacture method of sheet glass of low-reflection film, it is characterised in that, also possess after organoalkoxysilane is hydrolyzed, add described compound (A), the dispersion liquid that then adds hollow minute particle and the operation of modulating coating fluid.
13. have the manufacture method of the sheet glass of low-reflection film as claimed in claim 9, it is characterised in that, described hollow minute particle is hollow silica particles.
14. display unit, comprise framework, display unit and are configured at the sheet glass with low-reflection film according to any one of claim 1��8 of the display surface of described display unit.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011081719 | 2011-04-01 | ||
| JP2011081720 | 2011-04-01 | ||
| JP2011-081833 | 2011-04-01 | ||
| JP2011-081719 | 2011-04-01 | ||
| JP2011081833 | 2011-04-01 | ||
| JP2011-081720 | 2011-04-01 | ||
| PCT/JP2012/059002 WO2012137744A1 (en) | 2011-04-01 | 2012-04-02 | Glass plate with low reflective film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103476726A CN103476726A (en) | 2013-12-25 |
| CN103476726B true CN103476726B (en) | 2016-06-01 |
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| CN201280016572.8A Active CN103476726B (en) | 2011-04-01 | 2012-04-02 | With the sheet glass of low-reflection film |
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|---|---|
| JP (1) | JP6020444B2 (en) |
| KR (1) | KR101884961B1 (en) |
| CN (1) | CN103476726B (en) |
| DE (1) | DE112012001546B4 (en) |
| TW (1) | TWI572481B (en) |
| WO (1) | WO2012137744A1 (en) |
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| US9957609B2 (en) | 2011-11-30 | 2018-05-01 | Corning Incorporated | Process for making of glass articles with optical and easy-to-clean coatings |
| US10077207B2 (en) | 2011-11-30 | 2018-09-18 | Corning Incorporated | Optical coating method, apparatus and product |
| EP3696293A1 (en) | 2011-11-30 | 2020-08-19 | Corning Incorporated | Optical coating method, apparatus and product |
| JP6174378B2 (en) * | 2013-05-30 | 2017-08-02 | リンテック株式会社 | Anti-glare hard coat film |
| US9206322B2 (en) | 2013-09-27 | 2015-12-08 | National Taiwan University Of Science And Technology | Non-fluorinated coating materials with anti-fingerprint property, and evaluation method thereof |
| JP6617699B2 (en) * | 2014-05-08 | 2019-12-11 | Ａｇｃ株式会社 | Glass article |
| CN111718131B (en) * | 2014-07-16 | 2023-04-25 | Ａｇｃ株式会社 | Cover glass |
| CN105647363B (en) * | 2016-01-18 | 2018-03-16 | 杭州启俄科技有限公司 | A kind of low-surface-energy composition and its application |
| JP2018075783A (en) * | 2016-11-10 | 2018-05-17 | 東レ株式会社 | Laminate |
| JP2018197183A (en) * | 2017-05-23 | 2018-12-13 | Ａｇｃ株式会社 | Glass article, and display unit |
| JP7067900B2 (en) * | 2017-11-06 | 2022-05-16 | リンテック株式会社 | Coat film |
| KR102075687B1 (en) * | 2019-06-05 | 2020-02-10 | 주식회사 이건창호 | Architectural glass panel with uniform color |
| MX2022011145A (en) * | 2020-03-11 | 2022-10-13 | Nippon Sheet Glass Co Ltd | Greenhouse, and coating-film-attached glass plate. |
| US20230193070A1 (en) * | 2020-05-14 | 2023-06-22 | 3M Innovative Properties Company | Fluorinated coupling agents and fluorinated (co)polymer layers made using the same |
| KR20220147377A (en) | 2021-04-27 | 2022-11-03 | 주식회사 에스폴리텍 | Functional sheet with excellent uv protection and anti-reflection properties |
| JP2023177176A (en) * | 2022-06-01 | 2023-12-13 | 日本板硝子株式会社 | Low reflective member, and coating liquid of low reflective film |
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| CN101957461A (en) * | 2003-12-26 | 2011-01-26 | 富士胶片株式会社 | Antireflection film, polarizing plate, method for producing them, liquid crystal display element, liquid crystal display device, and image display device |
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| JP4031624B2 (en) * | 2000-06-23 | 2008-01-09 | 株式会社東芝 | Substrate with transparent coating, coating liquid for forming transparent coating, and display device |
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- 2012-04-02 DE DE112012001546.0T patent/DE112012001546B4/en active Active
- 2012-04-02 WO PCT/JP2012/059002 patent/WO2012137744A1/en active Application Filing
- 2012-04-02 JP JP2013508865A patent/JP6020444B2/en active Active
- 2012-04-02 CN CN201280016572.8A patent/CN103476726B/en active Active
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| CN101957461A (en) * | 2003-12-26 | 2011-01-26 | 富士胶片株式会社 | Antireflection film, polarizing plate, method for producing them, liquid crystal display element, liquid crystal display device, and image display device |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20140011348A (en) | 2014-01-28 |
| JPWO2012137744A1 (en) | 2014-07-28 |
| TWI572481B (en) | 2017-03-01 |
| JP6020444B2 (en) | 2016-11-02 |
| DE112012001546B4 (en) | 2023-02-16 |
| KR101884961B1 (en) | 2018-08-02 |
| CN103476726A (en) | 2013-12-25 |
| WO2012137744A1 (en) | 2012-10-11 |
| TW201244924A (en) | 2012-11-16 |
| DE112012001546T5 (en) | 2014-01-16 |
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