CN103476726A - Glass plate with low reflective film - Google Patents

Glass plate with low reflective film Download PDF

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Publication number
CN103476726A
CN103476726A CN2012800165728A CN201280016572A CN103476726A CN 103476726 A CN103476726 A CN 103476726A CN 2012800165728 A CN2012800165728 A CN 2012800165728A CN 201280016572 A CN201280016572 A CN 201280016572A CN 103476726 A CN103476726 A CN 103476726A
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China
Prior art keywords
low
reflection film
sheet glass
fluorine
minute particle
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Granted
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CN2012800165728A
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Chinese (zh)
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CN103476726B (en
Inventor
阿部启介
桑原雄一
河合洋平
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AGC Inc
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Asahi Glass Co Ltd
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Publication of CN103476726A publication Critical patent/CN103476726A/en
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

Abstract

The present invention relates to a glass plate (10) with a low reflective film having a low reflective film (14) of a monolayer containing a matrix and hollow fine particles on the surface of a glass plate (12), wherein the lowest reflectance of the low reflective film (14) within the range of a wavelength of 300 to 1,200 nm is 1.7% or lower, the water contact angle in the surface of the low reflective film (14) is 97 DEG or more, the oleic acid contact angle in the surface of the low reflective film (14) is 50 DEG or more, and the oleic acid sliding angle in the surface of the low reflective film (14) is 25 DEG or less. The present invention provides a glass plate with a low reflective film of a monolayer having a sufficiently low reflectance and good removal performance of oil stain, a method for producing the glass plate with a low reflective film, and a display device having the glass plate with a low reflective film.

Description

Sheet glass with low-reflection film
Technical field
The present invention relates to the sheet glass of low-reflection film, manufacture method with the sheet glass of low-reflection film, display unit and for the sheet glass with low-reflection film of display unit.
Background technology
What have low-reflection film on the surface of sheet glass is used as the cover glass etc. of the cover glass of solar cell, various indicating meter and front plate thereof, various window glass or touch-screen with the sheet glass of low-reflection film.
In the various display unit of the giant display of the miniscope of mobile phone or mobile information terminal etc., various televisors etc. or touch-screen etc.; in order in the protection indicating meter, to improve aesthetics, use cover glass (protective glass) in the front of display unit more and more.So, in order to promote the visuognosis degree of the shown image of display unit, use the sheet glass with low-reflection film with anti-visible ray reflectance coating as cover glass.
Wherein, contacted by staff continually for the sheet glass with low-reflection film of various indicating meters, window glass for automobile, touch-screen etc. or for the aforementioned sheet glass with low-reflection film of aforementioned display, require to have the removability of the grease spot of fingerprint etc.
As giving the method with grease spot removability with the sheet glass of low-reflection film, having of being widely known by the people attaches the method for the film that prevents the grease spot or the method (patent documentation 1) of coating anti-pollution layer on anti-reflection layer on its surface.
But, attach in the situation that have the surface of the sheet glass of low-reflection film the film that prevents the grease spot, due to the manufacturing process that increases film, the operations such as attaching operation of film, produce productivity and reduce, because attaching inequality, cause exterior quality to descend or along with film attaches the problem of cost rising etc.And in the situation that coating anti-pollution layer on anti-reflection layer, also produce the problem of degradation under productivity.
The prior art document
Patent documentation
The special table of patent documentation 1 Japanese Patent 2002-506887 communique
Summary of the invention
Invent technical problem to be solved
The invention provides a kind of reflectivity enough low and grease spot removability is good, surface sheet glass has the individual layer low-reflection film with the sheet glass of low-reflection film, can manufacture the manufacture method of the described sheet glass with low-reflection film and have the display unit of the described sheet glass with low-reflection film.
The technical scheme that the technical solution problem adopts
Sheet glass with low-reflection film of the present invention is the sheet glass with low-reflection film that has the individual layer low-reflection film that comprises matrix and hollow minute particle on the surface of sheet glass, wherein, the minimum reflectivity of the described low-reflection film in wavelength 300～1200nm scope 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 means above-mentioned numerical range usings and comprises that the numerical value of record is used as the implication of lower value and higher limit before and after it, as long as no being particularly limited, below "～" in this specification sheets all with identical meanings, use.
Of the present invention with in the sheet glass of low-reflection film, the individual layer low-reflection film refers to the homogeneous of giving low reflection function or the film of homogeneous or inhomogeneous one deck structure in fact.In addition, the sheet glass with 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, in the glass surface of the opposition side that does not form 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, conducting film, near infrared ray blocking film, anti electromagnetic wave film, hue adjustment film, the binding property that can form one deck and even multilayer improved film, weather resistance improves film, electrostatic prevention film, other various required function film.
The ratio of the fluorine element on the described low-reflection film surface of preferably being measured by X-ray photoelectron spectroscopy is 3～20 atom %.
The arithmetic average roughness (Ra) on the described low-reflection film surface of preferably being measured by the 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 be take silicon-dioxide as principal constituent and is had the structure from the 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 water-disintegrable silylation.
Preferred described fluorine-containing ether compound is the represented compound (A) of following formula (A),
Ｒ Ｆ1Ｏ（ＣＦ 2ＣＦ 2Ｏ） ａＣＦ 2－（Ｑ） ｂ（－（ＣＨ 2） ｄ－ＳｉＬ ｐＲ 3－ｐ） ｃ···（A）
Wherein, R f1for 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 be containing-OCF 2the group of O-structure,
The integer that a is 1～200,
B is 0 or 1,
Q is not exist in 0 o'clock at b, at b, is within 1 o'clock, to be divalence or trivalent concatenating group,
C does not exist or Q is 1 while being bivalence linking base at Q, when Q is the trivalent concatenating group, is 2,
The integer that d is 2～6,
L is hydrolization group,
R is hydrogen atom or monovalence alkyl,
The integer that p is 1～3.
Preferred described hollow minute particle is hollow silica particles.
The manufacture method of the sheet glass with low-reflection film of the present invention is the manufacture method that has the sheet glass with low-reflection film of the individual layer low-reflection film that comprises matrix and hollow minute particle on the surface of sheet glass, possess: will comprise matrix precursor, the coating fluid of hollow minute particle and solvent is coated the surface of sheet glass, the operation of being 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 water-disintegrable silylation, hollow minute particle in described coating fluid and silica precursor (SiO 2conversion) mass ratio (hollow minute particle/SiO 2) be 6/4～4/6, in coating fluid, the ratio of fluorine-containing ether compound is with respect to hollow minute particle and silica precursor (SiO 2conversion) total amount (100 quality %) is 0.8～3.0 quality %.
In addition, above-mentioned " fluorine-containing ether compound and/or its hydrolytic condensate " refers at least one of the hydrolytic condensate that is selected from fluorine-containing ether compound and fluorine-containing ether compound in this manual.
Preferred described fluorine-containing ether compound is the represented compound (A) of following formula (A),
Ｒ Ｆ1Ｏ（ＣＦ 2ＣＦ 2Ｏ） ａＣＦ 2－（Ｑ） ｂ（－（ＣＨ 2） ｄ－ＳｉＬ ｐＲ 3－ｐ） ｃ···（A）
R f1, a, b, Q, c, d, L, R and p have and aforementioned identical implication.
The hydrolytic condensate that preferred described silica precursor is organoalkoxysilane.
Preferably, in the modulating process of the coating fluid in the manufacture method of the sheet glass with low-reflection film of the present invention, after the organoalkoxysilane hydrolysis, add compound (A), then add the dispersion liquid of hollow minute particle and make coating fluid.
Preferred described hollow minute particle is hollow silica particles.
The present invention also provides display unit, comprise framework, display unit, the sheet glass with low-reflection film with the display surface that is disposed at described display unit, the described sheet glass with low-reflection film is the sheet glass with low-reflection film that has the individual layer low-reflection film that comprises matrix and hollow minute particle on the surface of sheet glass, the minimum reflectivity of the described low-reflection film in wavelength 300～1200nm scope 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, the present invention also provides 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 that has the individual layer low-reflection film that comprises matrix and hollow minute particle on the surface of sheet glass, the minimum reflectivity of the described low-reflection film in wavelength 300～1200nm scope 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 to say, display unit of the present invention is characterised in that, comprises framework, display unit and is disposed at the described sheet glass with low-reflection film of the display surface of described display unit.
The present invention also provides the described sheet glass with low-reflection film for display unit.
Described display unit with the sheet glass of low-reflection film and the sheet glass with low-reflection film for showing, described low-reflection film all be formed at display unit the outside, be the outermost of beholder's side or operator's side.
The invention effect
Sheet glass with low-reflection film of the present invention has enough good individual layer low-reflection films of low and grease spot removability of reflectivity on the surface of sheet glass.
By the manufacture method of the sheet glass with low-reflection film of the present invention, the surface that can be manufactured on sheet glass has enough sheet glass with low-reflection film of the good individual layer low-reflection film of low and grease spot removability of reflectivity.
Display unit of the present invention be possess have reflectivity enough the sheet glass of the good individual layer low-reflection film of low and grease spot removability as the display unit of cover glass.
The simple declaration of accompanying drawing
Fig. 1 shows the sheet glass with low-reflection film of the present invention and for the sectional view of an example of the sheet glass with low-reflection film of display unit.
Fig. 2 is routine 37(embodiment) the scanning electron microscope photo of the section with the sheet glass of low-reflection film.
Fig. 3 is the sectional view that shows an example of display unit of the present invention.
Embodiment
Fig. 1 is the sectional view that shows an example of the sheet glass with low-reflection film of the present invention and the sheet glass (being designated hereinafter simply as the sheet glass with low-reflection film) with low-reflection film for display unit of the present invention.Sheet glass 10 with low-reflection film has sheet glass 12 and the low-reflection film 14 that is formed at sheet glass 12 surfaces.
Fig. 3 is the sectional view that shows an example of display unit 100 of the present invention.Display unit 100 comprise be designated hereinafter simply as the sheet glass 10 with low-reflection film for display unit with the sheet glass 10(of low-reflection film), display unit 20 and framework 30.Sheet glass 10 with low-reflection film has sheet glass 12 and the low-reflection film 14 that is formed at sheet glass 12 surfaces.Low-reflection film 14 is formed on the face of tossing about of the face relative with display unit of sheet glass.
In Fig. 1,3, with the upper face side of the low-reflection film 14 of the sheet glass 10 of low-reflection film become display unit the outside, be beholder's side or operator's side.
Display unit of the present invention comprises the various display unit of the giant display of the miniscope of mobile phone or mobile information terminal etc., various televisors etc. or touch-screen etc.Particularly, mobile phone, mobile information terminal or touch-screen etc. are because the display surface of display unit is directly frequent by the chance that staff contacted, thereby are exemplified as the preferred concrete example had with the display unit of the present invention of the sheet glass of low-reflection film of fingerprint removability excellence.
As display unit, can exemplify liquid crystal display component, plasma display parts or organic EL display unit etc.
Framework is the case shape parts of taking in display unit 20 and having the sheet glass 10 of low-reflection film, and material can exemplify resin or metal etc.
(sheet glass)
Sheet glass 12 can exemplify such as soda-lime glass, borosilicate glass, alumina silicate glass or non-alkali glass etc.In addition, can be also by the level and smooth sheet glass of the shapings such as float glass process, or the irregular figured glass of surperficial tool.In addition, the specific refractory power of sheet glass 12 from and low-reflection film between the relation of specific refractory power consider, be preferably 1.45～1.60.
The surface of sheet glass 12 can be pre-formed low-reflection film 14 layer in addition of basic metal blocking layer, undercoat etc.
(low-reflection film)
Low-reflection film 14 is for example by once being coated with low-reflection film described later, to form form with coating fluid, unitary film that comprise matrix and hollow minute particle.But low-reflection film 14 is by repeatedly repeatedly being coated with low-reflection film and forming with coating fluid and film forming is also harmless, this film can regard as performance as the single layer structure of the function of low-reflection film or in fact the structure of individual layer get final product.
As matrix, lower from specific refractory power, can obtain antiradar reflectivity, chemically excellent in stability, with the angle of the adaptation excellence of sheet glass 12, consider, preferably take silicon-dioxide as principal constituent, contain a small amount of composition from the structure of fluorine-containing ether compound that has again.In matrix, except thering is the composition from the structure of fluorine-containing ether compound, preferably by silicon-dioxide, formed in fact.What is called be take silicon-dioxide more than principal constituent refers to that the ratio of silicon-dioxide accounts for 90 quality % in matrix (100 quality %), is formed and is referred to except the structure from compound described later (A) and inevitably only consist of silicon-dioxide impurity by silicon-dioxide in fact.
In addition, from the angle of grease spot removability excellence, consider, matrix optimization 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 water-disintegrable silylation.
As matrix, can exemplify the burned material that is selected from following matrix precursor (a) and (b) and at least one matrix precursor (c) etc., from the angle of grease spot removability excellence, consider, preferably the burned material of matrix precursor (a).
(a) matrix precursor that comprises silica precursor described later and fluorine-containing ether compound described later.
(b) matrix precursor that comprises the hydrolytic condensate between silica precursor described later, fluorine-containing ether compound described later and fluorine-containing ether compound.
(c) comprise 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, can exemplify Al 2o 3, SiO 2, SnO 2, TiO 2, ZrO 2, ZnO, CeO 2, containing the SnO of Sb x(ATO) In that, contains Sn 2o 3(ITO), RuO 2deng.Can be used alone wherein a kind of, also can and with two or more.
In addition, as the shape of hollow minute particle, can exemplify spherical, ellipticity, needle-like, tabular, bar-shaped, coniform, cylindric, cubic, rectangular-shaped, diamond-like, starlike, irregularly shaped etc.
In addition, hollow minute particle can each particulate independently state exist, also can connect to chain by each particulate, or each microparticle agglutination.
As hollow minute particle, low from the specific refractory power of low-reflection film 14, can obtain antiradar reflectivity, chemically excellent in stability, consider hollow silica particles preferably with the angle of the adaptation excellence of sheet glass 12.
The average primary particle diameter of hollow silica particles is preferably 5～150nm, 50～100nm more preferably.If the average primary particle diameter of hollow silica particles is more than 5nm, the reflectivity of low-reflection film 14 becomes enough low.If the average primary particle diameter of hollow silica particles is below 150nm, the haze value of low-reflection film 14 can reduce.
Average primary particle diameter by selecting at random 100 particulates from electron micrograph, measure the particle diameter of each particulate, the mean value of getting the particle diameter of 100 particulates is obtained.
The minimum reflectivity of the low-reflection film 14 in wavelength 300～1200nm scope 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%, the sheet glass 10 with low-reflection film fully meets the required antiradar reflectivities such as various indicating meters, window glass for automobile or touch-screen.If the minimum reflectivity of low-reflection film 14 is greater than 1.7%, there is the situation of low reflection characteristic deficiency.
The water contact angle on low-reflection film 14 surfaces more than 97 °, preferably 95 °～121 °, more preferably 97 °～109 °, further preferably 97 °～99 °.
The oleic acid contact angle on low-reflection film 14 surfaces more than 50 °, preferably 50 °～90 °, more preferably 52 °～87 °, particularly preferably 55 °～85 °.
The oleic acid on low-reflection film 14 surfaces tumble angle below 25 °, preferably 5 °～25 °, more preferably 5 °～20 °, further preferably 6 °～10 °.
Meet aforementioned range if the water contact angle on low-reflection film 14 surfaces, oleic acid contact angle and oleic acid tumble angle, the grease spot removability on low-reflection film 14 surfaces becomes good simultaneously.
The ratio of the fluorine element on described low-reflection film 14 surfaces of being measured by X-ray photoelectron spectroscopy is preferably 3～20 atom %, more preferably 5～18 atom %, 5～16 atom % more preferably.The ratio of the fluorine element on low-reflection film 14 surfaces mean from the structure of the fluorochemicalss such as compound described later (A) 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 surfaces is more than 3 atom %, grease spot removability further improves.If the ratio of the fluorine element on low-reflection film 14 surfaces is below 20 atom %, because in the situation that do not affect the optical design of film, maintaining low reflectivity preferably.In addition, X-ray photoelectron spectroscopy is owing to being to observe the photoelectronic method of escaping from specimen surface because of the irradiation of X ray, so analytical results is the photoelectronic degree of depth of escaping that can observe, the more specifically analysis information to the outermost surface of approximately several nm～tens nm degree of depth from the outermost surface of the air side of low-reflection film.
The arithmetic average roughness (Ra) on low-reflection film 14 surfaces of being measured by the scanning type probe microscope device is preferably 3.0～5.0nm, more preferably 3.0～4.5nm, 3.0～4.0nm more preferably.If the arithmetic average roughness (Ra) on low-reflection film 14 surfaces more than 3.0nm, demonstrates very trickle concavo-convex of formation, water-and oil-repellency easily improves.If the arithmetic average roughness (Ra) on low-reflection film 14 surfaces is below 5.0nm, grease spot removability further improves.
The specific refractory power of low-reflection film 14 is preferably 1.20～1.46, 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, 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, the reflectivity of low-reflection film 14 fully reduces.
By the individual layer low-reflection film 14 that is formed at sheet glass 12 surfaces, the refractive index n s by (being so-called bottom reflection rate (ボ ト system the reflectivity)) Rmin of the minimum reflectivity in wavelength 30～1200nm scope of spectrophotometric determination and sheet glass 12 calculates via following formula (1) refractive index n of low-reflection film 14.
Ｒｍｉｎ＝（ｎ－ｎｓ） 2／（ｎ＋ｎｓ） 2···（1）。
The thickness of low-reflection film 14 is preferably 80～100nm, 85～95nm more preferably.If the thickness of low-reflection film 14, more than 80nm, presents the weather resistance of low-reflection film 14.If the thickness of low-reflection film 14 below 100nm, though according to the specific refractory power of film used, change, preferred because presenting as the low reflectivity of unitary film.
The image that the thickness of low-reflection film 14 obtains by the section of observing low-reflection film 14 with scanning electron microscope is measured.
(manufacture method of having the sheet glass of low-reflection film)
Sheet glass 10 with low-reflection film of the present invention can coat the surface of sheet glass 12 by the coating fluid that for example will be used to form low-reflection film 14, according to requiredly carrying out preheating, manufacturing finally by burning till.
Coating fluid comprises matrix precursor, hollow minute particle and solvent.
Coating fluid can comprise tensio-active agent for improving planarization or for metallic compound of the weather resistance that improves low-reflection film 14 etc.
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 water-disintegrable silylation.
The hydrolytic condensate of described fluorine-containing ether compound can be the hydrolytic condensate between the fluorine-containing ether compound, can be also as the organoalkoxysilane of silica precursor and the hydrolytic condensate between the fluorine-containing ether compound.
As matrix precursor, specifically can exemplify and be selected from following matrix precursor (a) and (b) and at least one matrix precursor (c), from the angle of the grease spot removability excellence of low-reflection film 14, consider, be more preferably matrix precursor (a).
(a) matrix precursor that comprises silica precursor and fluorine-containing ether compound.
(b) matrix precursor of the hydrolytic condensate that comprises silica precursor, fluorine-containing ether compound and compound (A).
(c) comprise 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, can exemplify the hydrolytic condensate (sol-gel silica) of organoalkoxysilane, organoalkoxysilane or silazane etc., from the angle of each characteristic of low-reflection film 14, consider, preferably the hydrolytic condensate of organoalkoxysilane.
As organoalkoxysilane, can exemplify tetraalkoxysilane (tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane or four butoxy silanes etc.), organoalkoxysilane (perfluor polyether triethoxyl silane etc.) with perfluor polyether base, organoalkoxysilane (perfluor ethyl triethoxysilane etc.) with perfluoroalkyl, organoalkoxysilane (vinyltrimethoxy silane or vinyltriethoxysilane etc.) with vinyl, organoalkoxysilane (2-(3 with epoxy group(ing), the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 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, under the occasion of tetraalkoxysilane, is carried out by the water more than 4 times moles with organoalkoxysilane with as acid or the alkali of catalyzer.As acid, can exemplify 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.).As alkali, can exemplify ammonia, sodium hydroxide or potassium hydroxide etc.As catalyzer, consider preferably acid from the angle of the prolonged preservation of the hydrolytic condensate of organoalkoxysilane.Catalyzer used in hydrolysis as organoalkoxysilane, preferably do not hinder the catalyzer of the dispersion of hollow minute particle.
The fluorine-containing ether compound can have water-disintegrable silylation at side's end of main chain, also can all have water-disintegrable silylation at two side's ends of main chain.Consider preferably only at side's end of main chain, there is water-disintegrable silylation with the angle of wear-resisting wiping from fully giving low reflection layer.
So-called low reflection layer, refer to the outermost surface that is formed at film layer, be the outermost surface part of the film that directly contacts of fingerprint or spot.
The fluorine-containing ether compound can be single compound, can be also the different mixtures of more than two kinds such as poly-(oxygen perfluorinated alkylidene) chain, terminal group or concatenating group.
The number-average molecular weight of fluorine-containing ether compound is preferably 500～10000, more preferably 800～8000.If number-average molecular weight in aforementioned range, wear-resisting wiping excellence.From and the angle that forms the consistency between other composition of matrix precursor consider, 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 less, and the chemical bond between base material becomes more firm.Its reason thinks that the number of the water-disintegrable silylation that corresponding per unit molecular weight exists becomes many causes.But the confirmations such as the inventor, if number-average molecular weight is less than the lower value of aforementioned range, wear-resisting wiping easily descends.In addition, if number-average molecular weight surpasses the higher limit of above-mentioned scope, wear-resisting wiping decline.Its reason thinks that the reduced number due to the water-disintegrable silylation of corresponding per unit molecular weight existence causes the cause of impact increase.
The fluorine-containing ether compound has poly-(oxygen perfluorinated alkylidene) chain, so the content of fluorine atom is many.So, the low reflection layer of high, the wear-resisting wiping of the water-and oil-repellency that the fluorine-containing ether compound can form the initial stage or fingerprint spot removability excellence.
Water-disintegrable silylation ((SiL in the fluorine-containing ether compound mr 3-m) forming silanol group (Si-OH) through hydrolysis reaction, aforementioned silanol group forms Si-O-Si key or aforementioned silanol group and substrate surface hydroxyl (base material-OH) through intermolecular reaction forms chemical bond (base material-O-Si) through dehydration condensation.That is to say, the low reflection layer in the present invention comprises this compound with part or all water-disintegrable silylation of this compound through the state of hydrolysis reaction.
As the fluorine-containing ether compound, for example can exemplify compound (A).
Compound (A) is the represented compound of following formula (A).
Ｒ Ｆ1Ｏ（ＣＦ 2ＣＦ 2Ｏ） ａＣＦ 2－（Ｑ） ｂ（－（ＣＨ 2） ｄ－ＳｉＬ ｐＲ 3－ｐ） ｃ···（A）
R f1for 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 be containing-OCF 2the group of O-structure.
The integer that a is 1～200, be preferably 2～100 integer, more preferably 3～50 integer, 5～25 integer more preferably.
B is 0 or 1, is preferably 1.
Q is not exist in 0 o'clock at b, at b, is within 1 o'clock, to be divalence or trivalent concatenating group.
C does not exist or Q is 1 while being bivalence linking base at Q, when Q is the trivalent concatenating group, is 2.
The integer that d is 2～6.
R is hydrogen atom or monovalence alkyl.
L is hydrolization group.So-called hydrolization group is to form through the hydrolysis of Si-L base the group of Si-OH base.
As L, can exemplify alkoxyl group, acyloxy, ketoxime base, alkene oxygen base, amino, aminooxy, amide group, isocyanate group or halogen atom etc., from the angle of the easiness of the stability of compound (A) and hydrolysis, consider, preferably alkoxyl group, isocyanate group and halogen atom (particularly chlorine atom).As alkoxyl group, preferably the alkoxyl group of carbon number 1～3, be more preferably methoxy or ethoxy.In fluorochemicals, there are 2 in L when above, and L can be that identical group can be also different group, for identical group is preferred from the angle of easy acquisition.
The integer that p is 1～3.If p more than 1, can make by the condensation between the Si-OH base from the sound construction of compound (A) be incorporated into matrix.P is preferably 2 or 3, is particularly preferably 3.
As compound (A), from the angle of the synthetic easiness of grease spot removability and compound (A), consider, preferably following compound (A-1) or compound (A-2).
ＣＦ 3Ｏ（ＣＦ 2ＣＦ 2Ｏ） ａ1ＣＦ 2Ｃ（Ｏ）ＮＨ－（ＣＨ 2） 3－Ｓｉ（ＯＣＨ 3） 3···（A－1）。
ＣＦ 3Ｏ（ＣＦ 2ＣＦ 2Ｏ） ａ2ＣＦ 2ＣＨ 2Ｏ（ＣＨ 2） 3Ｓｉ（ＯＣＨ 3） 3···（A－2）。
Wherein, the integer that a1 and a2 are 5～25.
Do not exist-OCF of compound (A) 2therefore the O-structure, even under the existence of acid catalyst and under hot conditions, also can form the low-reflection film 14 of deteriorated patience excellence.
In addition, (the CF of compound (A) 2cF 2o) a structure is not have the CF that transport properties of molecules is reduced 3the alkylidene group 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 of inclusion compound (A) becomes the film of grease spot removability excellence.
Hollow minute particle in coating fluid and silica precursor (SiO 2conversion) mass ratio (hollow minute particle/SiO 2) be preferably 6/4～4/6.If the ratio of hollow minute particle is less than 6/4, the arithmetic average roughness (Ra) on low-reflection film 14 surfaces diminishes, and the grease spot removability of low-reflection film 14 rises.If the ratio of hollow minute particle is greater than 4/6, the specific refractory power step-down of low-reflection film 14, the reflectivity of low-reflection film 14 fully reduces.
In coating fluid, the ratio of fluorine-containing ether compound is with respect to hollow minute particle and silica precursor (SiO 2convert) total amount (100 quality %) be preferably 0.8～3.0 quality %, 1.0～1.8 quality % more preferably.If the ratio of fluorine-containing ether compound is more than 0.8 quality %, grease spot removability further rises.If below 2.0 quality %, can not occurring to concentrate because of the fluorine-containing ether compound part that is present in the film surface, the ratio of fluorine-containing ether compound do not cause the situations such as mist degree rising, thereby preferably.
As solvent, can exemplify the dispersion medium etc. of dispersion liquid of solvent, the hollow minute particle of the solution of matrix precursor.
As the solvent of the solution of the hydrolytic condensate of organoalkoxysilane, the preferably mixed solvent of water and alcohols (such as methyl alcohol, ethanol, Virahol, butanols or Pyranton etc.).
As the solvent of the solution of fluorine-containing ether compound, preferably organic solvent.Organic solvent can be that fluorine is organic solvent, can be also that non-fluorine is organic solvent, can also be the solvent that comprises the two.As aforementioned solvents, can exemplify methyl alcohol or ethanol etc.
Dispersion medium as the dispersion liquid of hollow minute particle, can exemplify water, alcohols, ketone, ethers, cellosolve class, ester class, glycol ethers, nitrogenous compound or sulfocompound etc.
Modulator approach as coating fluid, can exemplify the method for following method (α) to (γ), when coating fluid being coated to sheet glass 12 surface, the fluorine-containing ether compound floats the surface of filming, burnt till afterwards and concentrated from the structure of fluorine-containing ether compound the surface that is present in low-reflection film 14, from the angle of having given play to excellent grease spot removability, consider, preferably method (β).In addition, from the angle of the aggegation that suppresses hollow minute particle, consider, the dispersion liquid of hollow minute particle preferably adds after the solution dilution by matrix precursor.
(α) after the organoalkoxysilane in solution and fluorine-containing ether compound hydrolysis according to required method of being diluted, then adding the dispersion liquid of hollow minute particle with solvent.
(β) after the organoalkoxysilane in solution hydrolysis (preferably from hydrolysis starts after the time more than 2 hours) add the solution of fluorine-containing ether compound, according to required method of being diluted, then adding the dispersion liquid of hollow minute particle with solvent.
(γ) diluted, then added the solution of fluorine-containing ether compound, added again the method for the dispersion liquid of hollow minute particle with solvent after the organoalkoxysilane in solution hydrolysis.
As coating process, can exemplify known wet type coating method (such as spin-coating method, spraying method, dip coating, mould, being coated with method, curtain coating method, silk screen printing coating method, ink jet method, flow coat method, intaglio printing coating method, excellent painting method, offset printing coating method, slot coated method or rolling method etc.) etc.
Coating temperature is preferably room temperature～200 ℃, room temperature～150 ℃ more preferably.
Firing temperature preferably more than 30 ℃, more preferably 100～180 ℃, can suitably determine according to the material of sheet glass, particulate or matrix.
Firing time preferably more than 3 minutes, more preferably 10 minutes～60 minutes, can suitably determine according to the material of sheet glass, particulate or matrix.
The surface that sheet glass with low-reflection film of the present invention is sheet glass has the sheet glass with low-reflection film of the individual layer low-reflection film that comprises matrix and hollow minute particle, it is aforementioned hollow silica particles that preferred aforementioned matrix has from the structure of aforementioned fluorine-containing ether compound and aforementioned hollow minute particle, and more preferably aforementioned fluorine-containing ether compound is the represented compound (A) of following formula (A).
Manufacture on the surface of coating sheet glass by the coating fluid that will comprise matrix precursor, hollow minute particle and solvent with the sheet glass of low-reflection film of the present invention.
That is to say, the sheet glass with low-reflection film of the present invention has low-reflection film from the teeth outwards, 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 forms, 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 tetraalkoxysilane and the represented compound (A) of following formula (A), further preferably comprise matrix precursor, hollow silica particles and solvent, wherein matrix precursor comprises the hydrolytic condensate between tetraethoxysilane and the represented compound (A) of following formula (A).
Ｒ Ｆ1Ｏ（ＣＦ 2ＣＦ 2Ｏ） ａＣＦ 2－（Ｑ） ｂ（－（ＣＨ 2） ｄ－ＳｉＬ ｐＲ 3－ｐ） ｃ···（A）。
R f1, a, b, Q, c, d, L, R and p have and aforementioned identical implication.
(action effect)
Sheet glass with low-reflection film of the present invention described above is the sheet glass with low-reflection film that has the individual layer low-reflection film that comprises matrix and hollow minute particle on the surface of sheet glass, the minimum reflectivity of the aforementioned low-reflection film in wavelength 300～1200nm scope 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 grease spot removability is good.
The manufacture method of the sheet glass with low-reflection film of the present invention described above possesses coats the surface of sheet glass, the operation of being burnt till by the coating fluid that comprises matrix precursor, hollow minute particle and solvent, 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 water-disintegrable silylation, the hollow minute particle in coating fluid and silica precursor (SiO 2conversion) mass ratio (hollow minute particle/SiO 2) be 6/4～4/6, in coating fluid, the ratio of fluorine-containing ether compound is with respect to hollow minute particle and silica precursor (SiO 2convert) total amount (100 quality %) be 0.8～3.0 quality %, the reflectivity that the surface that therefore can manufacture sheet glass has a low-reflection film is the sheet glass with low-reflection film of the good individual layer low-reflection film of low and grease spot removability enough.
Display unit of the present invention described above comprises that the surface of sheet glass has the sheet glass with low-reflection film of the individual layer low-reflection film that comprises matrix and hollow minute particle.And, aforementioned with in the sheet glass of low-reflection film, the minimum reflectivity of the aforementioned low-reflection film in wavelength 300～1200nm scope 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 grease spot 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 is used spectrophotometer (Hitachi's system, model: U-4100) measure.The visual sense reflectivity is that the reflectivity of wavelength 380～780nm is multiplied by the reflectivity that weighting function obtains by equalization.
(minimum reflectivity)
Use spectrophotometer (Hitachi's system, model: U-4100) measure the reflectivity in wavelength 300～1200nm scope, obtain the minimum value (minimum reflectivity) of reflectivity.
(mist degree)
The mist degree of having the sheet glass of low-reflection film is used mist degree determinator (Bi Ke-Gartner company (BYK-Gardner society) system, Haze-guard Plus) to measure.
(water contact angle)
Place the approximately distilled water of 48 μ L of three places on the surface of low-reflection film, use contact angle meter (the consonance (Association of interface science Co., Ltd. and interface science society) system, FAMAS) measure water contact angle separately, obtain the mean value of 3 values.
(oleic acid contact angle)
Place the approximately oleic acid of 48 μ L of three places on the surface of low-reflection film, use contact angle meter (the consonance (Association of interface science Co., Ltd. and interface science society) system, FACE SLIDING ANGLE METER) measure oleic acid contact angle separately, obtain the mean value of 3 values.
(oleic acid tumbles angle)
To keep level with the sheet glass of low-reflection film, on the surface of low-reflection film, drip after the oleic acid of 48 μ L, slowly tilt with the sheet glass of low-reflection film, the sheet glass with low-reflection film when mensuration oleic acid starts to tumble and the angle (tumbling angle) of horizontal plane.As measurement result, " can't measure " means that oleic acid launches on substrate, even the sheet glass tilted with low-reflection film also can't observe the state of the movement of oleic acid etc.
(ratio of fluorine element)
For 3 sheet glass with low-reflection film of example 11,23 and 35, use x-ray photoelectron energy spectral apparatus (A Er Wacker process Co., Ltd. (ア Le バ ッ Network Off ァ イ society) system, Quantera SXM) to obtain the ratio of the fluorine element on low-reflection film surface.Make the ratio of fluorine element on low-reflection film surfaces with respect to the calibration curve of the ratio of the compound coating fluid (A) from the measurement results of 3.For the sheet glass with low-reflection film of other example except example 11,23 and 35, use the ratio of the compound (A) of calibration curve in coating fluid to obtain the ratio of the fluorine element on low-reflection film surface.
(arithmetic average roughness)
The arithmetic average roughness on low-reflection film surface (Ra) is used scanning type probe microscope device (SII Nanoentech Co., Ltd. (SII Na ノ テ Network ノ ロ ジ ー society) system, SPA400DFM) to measure.
(specific refractory power)
The refractive index n of low-reflection film is by the individual layer low-reflection film is calculated by following formula (1) with the refractive index n s of the minimum reflectivity Rmin in wavelength 300～1200nm scope of spectrophotometric determination and sheet glass.
Ｒｍｉｎ＝（ｎ－ｎｓ） 2／（ｎ＋ｎｓ） 2···（1）。
(grease spot tack)
Use permanent pen (Zebra Company (ゼ Block ラ society) system, mark's (registered trademark)) to draw straight line on the surface of low-reflection film, estimated according to following standard.
A: line all becomes drops, the state that can't clearly write fully.
B: the part of line becomes drops, the state that can be recognized as line.
C: can be drawn as line, can be recognized as clearly line.
(grease spot removability)
After having estimated grease spot tack, with the oily ink on wiping (kimwipe) paper wiping low-reflection film surface, according to following standard, estimated.
A: only wipe three times and wipe oily ink fully.
B: during wiping 10 times, substantially wipe, but slightly residual oiliness ink marks.
C: during wiping 30 times, the oily ink color slightly shoals, but substantially can't wipe.
D: during wiping 100 times, the oily ink color slightly shoals, but substantially can't wipe.
E: even wiping 100 times, the oily ink color is also fully unchanged.
(sheet glass)
As sheet glass, prepare soda-lime glass (Asahi Glass Co., Ltd (Asahi Glass 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).
The method that the embodiment 1 and 2 that No. 2009/008380th, compound (A-1) employing International Publication puts down in writing is manufactured.
(organoalkoxysilane)
As organoalkoxysilane, prepare solution (Junsei Chemical Co., Ltd. (the positive chemical society of Pure) 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, SiO 2conversion 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 (Play catalyst changes into society) system, hollow-particle colloidal sol, SiO2 conversion solid component concentration: 20 quality %, average primary particle diameter: 20nm, alcohol: 80 quality %.
Example 1
In the TEOS of 10g solution, 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, the solution that adds the compound (A-1) of 0.005g, stir after 15 minutes, mixed solvent (the Virahol: 30 quality %, 2-butanols: 25 quality %, ethanol: 8 quality %, Pyranton: 15 quality %, methyl alcohol: 17 quality %) that adds 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 spin coating (180rpm, 60 minutes), after the surface of sheet glass, is burnt till 30 minutes under 150 ℃, obtain the sheet glass with low-reflection film.The evaluation result of having the sheet glass of low-reflection film is shown in table 2.
Example 2
Except the rotating speed by spin coating is changed to 250rpm by 180rpm, and example 1 similarly makes the sheet glass with low-reflection film.The composition of coating fluid is shown in table 1, and the evaluation result of having the sheet glass of low-reflection film is shown in table 1.
Example 3～12
Except the composition by coating fluid changes to the composition shown in table 1, and example 1 and example 2 similarly make the sheet glass with low-reflection film.Estimate the aforementioned sheet glass with low-reflection film.The results are shown in table 2.Table 1
Figure BDA0000390216120000181
Table 2
Figure BDA0000390216120000191
Example 13～23
Except the ratio by compound (A-1) changes to the ratio shown in table 3, and example 1～12 similarly makes the sheet glass with low-reflection film.Estimate the aforementioned sheet glass with low-reflection film.The results are shown in table 4.
Table 3
Figure BDA0000390216120000201
Table 4
Figure BDA0000390216120000211
Example 24～34
Except the ratio by compound (A-1) changes to the ratio shown in table 5, and example 1～12 similarly makes the sheet glass with low-reflection film.Estimate the aforementioned sheet glass with low-reflection film.The results are shown in table 6.
Table 5
Table 6
Figure BDA0000390216120000231
Example 35～42
Except the composition by coating fluid changes to the composition shown in table 7, changes to opportunity before the TEOS hydrolysis by the interpolation of compound (A-1), and example 1～12 similarly makes the sheet glass with low-reflection film.Estimate the aforementioned sheet glass with low-reflection film.The results are shown in table 8.
Example 43～50
Except the interpolation by compound (A-1) change to opportunity the TEOS hydrolysis after 1 hour, and example 35～42 similarly makes the sheet glass with low-reflection film.Estimate the aforementioned sheet glass with low-reflection film.The results are shown in table 8.
Table 7
Figure BDA0000390216120000241
Table 8
Figure BDA0000390216120000251
Example 51～58
Except the interpolation by compound (A-1) change to opportunity the TEOS hydrolysis after 2 hours, and example 35～42 similarly makes the sheet glass with low-reflection film.Estimate the aforementioned sheet glass with low-reflection film.The results are shown in table 10.
Example 59～66
Except the interpolation by compound (A-1) changes to the TEOS hydrolysis opportunity after 2 hours and with after solvent cut, and example 35～42 similarly makes the sheet glass with low-reflection film.Estimate the aforementioned sheet glass with low-reflection film.The results are shown in table 10.
Table 9
Figure BDA0000390216120000271
Table 10
Figure BDA0000390216120000281
The scanning electron microscope photo of the section of the sheet glass with low-reflection film of example 37 is shown in Fig. 2.Shown in Fig. 2 be with the focused ion tractotomy with the sheet glass of low-reflection film the SEM picture of the multiplying power of 100000 times of film profile direction.The about 100nm of the thickness of low-reflection film, consist of hollow-particle and matrix components (silicon-dioxide and fluorine cpd).Confirm in film that it is can see the position of the emptying aperture of hollow-particle inside after hollow-particle is cut off that the part of emptying aperture is arranged.
Utilize possibility on industry
The sheet glass that sheet glass with low-reflection film of the present invention and the sheet glass with low-reflection film made by manufacture method of the present invention can be used as for various indicating meters, window glass for automobile or touch-screen etc. is used.
Display unit of the present invention can be used for various televisors, touch-screen, mobile phone or mobile information terminal etc.
In addition, quote that the Japanese patent application laid of filing an application in Japan on April 1st, 2011 is willing to that the Japanese patent application laid of filing an application in Japan on April 1st, No. 2011-081719 1 is willing to No. 2011-081720 here and the Japanese patent application laid of filing an application in Japan on April 1st, 2011 is willing to that the full content of specification sheets, claims, accompanying drawing and summary of No. 2011-081833 is as announcement of the present invention.
The explanation of symbol
10 sheet glass with low-reflection film
12 sheet glass
14 low-reflection films
100 display unit
20 display units
30 frameworks

Claims (15)

1. with the sheet glass of low-reflection film, be the sheet glass with low-reflection film that there is the individual layer low-reflection film that comprises matrix and hollow minute particle on the surface of sheet glass, wherein,
The minimum reflectivity of the described low-reflection film in wavelength 300～1200nm scope 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 °.
2. the sheet glass with low-reflection film as claimed in claim 1, is characterized in that, the described individual layer low-reflection film that comprises matrix and hollow minute particle is formed at least outermost layer of one side of described sheet glass.
3. the sheet glass with low-reflection film as claimed in claim 1 or 2, is characterized in that, the ratio of the fluorine element on the described low-reflection film surface of being measured by X-ray photoelectron spectroscopy is 3～20 atom %.
4. the sheet glass with low-reflection film as described as any one in claim 1～3, is characterized in that, the arithmetic average roughness (Ra) on the described low-reflection film surface of being measured by the scanning type probe microscope device is 3.0～5.0nm.
5. the sheet glass with low-reflection film as described as any one in claim 1～4, is characterized in that, the specific refractory power of described low-reflection film is 1.20～1.46.
6. the sheet glass with low-reflection film as described as any one in claim 1～5, it is characterized in that, described matrix be take silicon-dioxide as principal constituent and is had the structure from the 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 water-disintegrable silylation.
7. the sheet glass with low-reflection film as described as any one in claim 1～6, is characterized in that, described fluorine-containing ether compound is the represented compound (A) of following formula (A),
Ｒ Ｆ1Ｏ（ＣＦ 2ＣＦ 2Ｏ） ａＣＦ 2－（Ｑ） ｂ（－（ＣＨ 2） ｄ－ＳｉＬ ｐＲ 3－ｐ） ｃ···（A）
Wherein, R f1for 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 be containing-OCF 2the group of O-structure,
The integer that a is 1～200,
B is 0 or 1,
Q is not exist in 0 o'clock at b, at b, is within 1 o'clock, to be divalence or trivalent concatenating group,
C does not exist or Q is 1 while being bivalence linking base at Q, when Q is the trivalent concatenating group, is 2,
The integer that d is 2～6,
L is hydrolization group,
R is hydrogen atom or monovalence alkyl,
The integer that p is 1～3.
8. the sheet glass with low-reflection film as described as any one in claim 1～7, is characterized in that, described hollow minute particle is hollow silica particles.
9. having the manufacture method of the sheet glass of low-reflection film, is the manufacture method that has the sheet glass with low-reflection film of the individual layer low-reflection film that comprises matrix and hollow minute particle on the surface of sheet glass, possesses:
The operation that the coating fluid that will comprise matrix precursor, hollow minute particle and solvent is coated the surface of sheet glass, 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 water-disintegrable silylation,
Mass ratio (hollow minute particle/the SiO of the hollow minute particle in described coating fluid and silica precursor (SiO2 conversion) 2) be 6/4～4/6,
In coating fluid, the ratio of fluorine-containing ether compound is with respect to hollow minute particle and silica precursor (SiO 2conversion) total amount (100 quality %) is 0.8～3.0 quality %.
10. the manufacture method of the sheet glass with low-reflection film as claimed in claim 9, is characterized in that, described fluorine-containing ether compound is the represented compound (A) of following formula (A),
Ｒ Ｆ1Ｏ（ＣＦ 2ＣＦ 2Ｏ） ａＣＦ 2－（Ｑ） ｂ（－（ＣＨ 2） ｄ－ＳｉＬ ｐＲ 3－ｐ） ｃ···（A）
Wherein, R f1for 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 be containing-OCF 2the group of O-structure,
The integer that a is 1～200,
B is 0 or 1,
Q is not exist in 0 o'clock at b, at b, is within 1 o'clock, to be divalence or trivalent concatenating group,
C does not exist or Q is 1 while being bivalence linking base at Q, when Q is the trivalent concatenating group, is 2,
The integer that d is 2～6,
L is hydrolization group,
R is hydrogen atom or monovalence alkyl,
The integer that p is 1～3.
11. the manufacture method of the sheet glass with low-reflection film as described as claim 9 or 10, is characterized in that the hydrolytic condensate that described silica precursor is organoalkoxysilane.
12. the manufacture method of the sheet glass with low-reflection film as claimed in claim 11, is characterized in that, also possesses to add described compound (A) after the organoalkoxysilane hydrolysis, then add the dispersion liquid of hollow minute particle and the operation of modulating coating fluid.
13. the manufacture method of the sheet glass with low-reflection film as described as any one in claim 9～12 is characterized in that described hollow minute particle is hollow silica particles.
14. display unit, comprise framework, display unit and be disposed at the described sheet glass with low-reflection film of any one in the claim 1～8 of display surface of described display unit.
15. the sheet glass with low-reflection film as described as any one in claim 1～8, is characterized in that, for display unit.
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