CN104955783B - Transparent base with anti-soil film - Google Patents

Transparent base with anti-soil film Download PDF

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Publication number
CN104955783B
CN104955783B CN201480006778.1A CN201480006778A CN104955783B CN 104955783 B CN104955783 B CN 104955783B CN 201480006778 A CN201480006778 A CN 201480006778A CN 104955783 B CN104955783 B CN 104955783B
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Prior art keywords
film
transparent base
interarea
soil film
soil
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CN104955783A (en
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藤井健辅
宫村贤郎
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AGC Inc
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Asahi Glass Co Ltd
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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
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • 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
    • C03C2217/77—Coatings having a rough surface

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Liquid Crystal (AREA)
  • Optical Elements Other Than Lenses (AREA)

Abstract

The present invention provides a kind of transparent base with anti-soil film, and it has：Transparent base, the transparent base has the first interarea and second interarea relative with first interarea, and implements anti-dazzle processing on the surface of first interarea；With fluorine-containing organic silicon compound overlay film, the fluorine-containing organic silicon compound overlay film is the anti-soil film for the first interarea side for being arranged on the transparent base；The surface roughness RMS of the anti-soil film is more than 0.05 μm and less than 0.25 μm, and the average length RSm of roughness curve key element is more than 10 μm and less than 40 μm.

Description

Transparent base with anti-soil film
Technical field
The present invention relates to the transparent base with anti-soil film.
Background technology
In recent years, it is especially in mancarried device, vehicle-mounted equipment to use the various display devices such as liquid crystal display more. In such display device, as its The lid component, all the time using the composition for being configured with transparent base.In addition, it is also known that will Substrate obtained from contact panel with transparency electrode is integrated with protective glass is formed.
For such display device, the chance on the touching transparent base such as finger of people surface is more, in the finger of people During Deng touching, grease etc. is easily adhered on transparent base surface.Moreover, when grease etc. adheres to, visuality can be influenceed, therefore Use the transparent base that antifouling process is implemented on the surface of transparent base.
As the transparent base for implementing antifouling process on the surface, such as Patent Document 1 discloses a kind of water repellency Glass, it is provided with water repellent layer on the glass baseplate surface with concaveconvex shape.
In addition, for the water repellency glass for being provided with water repellent layer, because the adhesive tension of water repellent and glass is weak, thus Be difficult to keep water repellency, therefore in order to improve its durability, studying always the surface configuration of glass substrate is made it is predetermined The method (such as patent document 2) of shape.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 07-126041 publications
Patent document 2：Japanese Unexamined Patent Publication 11-171594 publications
The content of the invention
Invent problem to be solved
However, the water repellency glass of patent document 2 is for the purpose of the purposes such as windshield, glass pane plate and the glass of exploitation Glass, the transparent base for not being intended to be display device etc. use.
Therefore, use the water repellency glass as the The lid component of the display devices such as liquid crystal display or with contact panel The protective glass of transparency electrode integration in use, due to almost there is no an anti-dazzle characteristic, therefore the light around mapping be present so that Visual the problem of reducing of display portion.
In addition, as described above, the water repellency glass of patent document 2 be designed for the human hands such as glass pane touching chance it is few Part water repellency glass, therefore as upper frequency is possible to as display device by human hand touching The lid component or The substrate integrated with contact panel is in use, durability is insufficient.
In view of problem possessed by above-mentioned prior art, it is an object of the present invention to provide one kind to have anti-dazzle characteristic same When improve anti-soil film durability the transparent base with anti-soil film.
The means used to solve the problem
In order to solve the above problems, the present invention provides a kind of transparent base with anti-soil film, and it has：
Transparent base, the transparent base have the first interarea and second interarea relative with first interarea, and The surface of first interarea implements anti-dazzle processing；With
Fluorine-containing organic silicon compound overlay film, the fluorine-containing organic silicon compound overlay film are the institute for being arranged on the transparent base State the anti-soil film of the first interarea side；
The surface roughness RMS of the anti-soil film is more than 0.05 μm and less than 0.25 μm, and roughness curve key element Average length RSm is more than 10 μm and less than 40 μm.
Invention effect
In the present invention, using the teaching of the invention it is possible to provide a kind of durability for improving anti-soil film simultaneously with anti-dazzle characteristic with anti-soil film Transparent base.
Brief description of the drawings
Fig. 1 is the explanation figure of the composition of the transparent base with anti-soil film of the 1st embodiment of the present invention.
Fig. 2 is the explanation figure of the composition of the transparent base with anti-soil film of the 2nd embodiment of the present invention.
Embodiment
The mode for implementing the present invention is described with reference to the accompanying drawings below, but the present invention is not limited to following implementations Mode, various modifications and displacement can be imposed to following embodiments without departing from the present invention.
1st embodiment
In the present embodiment, the transparent base with anti-soil film of the present invention is illustrated.
The transparent base with anti-soil film of present embodiment has transparent base and fluorine-containing organic silicon compound overlay film, described Transparent base has the first interarea and second interarea relative with above-mentioned first interarea, and implements on the surface of above-mentioned first interarea Anti-dazzle processing, the fluorine-containing organic silicon compound overlay film be arranged on above-mentioned transparent base above-mentioned first interarea side it is antifouling Film.Moreover, the above-mentioned transparent base with anti-soil film is characterised by：The surface roughness RMS of above-mentioned anti-soil film be 0.05 μm with It is upper and less than 0.25 μm, and the average length RSm of roughness curve key element is more than 10 μm and less than 40 μm.
Illustrate the transparent base with anti-soil film of present embodiment using Fig. 1.Fig. 1 schematically shows present embodiment The sectional view of transparent base with anti-soil film, have and be configured with the composition of anti-soil film 12 in the first interarea side of transparent base 11. Each component for forming the transparent base with anti-soil film is illustrated below.
First, the material as transparent base 11 is not particularly limited, and can utilize transmissive at least for the various of visible ray Bright matrix.It can enumerate for example：The various materials such as plastic base, glass substrate.Wherein, from viewpoints such as the transparency, intensity, Transparent base is preferably glass substrate.In this case, the species of glass is not particularly limited, can utilize alkali-free glass, The various glass such as soda-lime glass, alumina silicate glass.Wherein, go out from the viewpoint of the adhesiveness of the layer (film) with being disposed above Hair, preferably using soda-lime glass.
In the case that transparent base 11 is glass substrate, from the viewpoint of the intensity of transparent base in itself, preferably use By alumina silicate glass by the (such as " Dragontrail (registrars of hardened glass substrate obtained from chemical intensification treatment Mark) " etc.).
Chemical intensification treatment refers to the small basic ion of the ionic radius of glass surface (such as sodium ion) being replaced as ion The processing of the big basic ion of radius (such as potassium ion).For example, the glass containing sodium ion is entered with the fused salt containing potassium ion Row processing, it is possible thereby to carry out chemical enhanced.The group of the compressive stress layer of glass baseplate surface after such chemical intensification treatment It is slightly different into the composition before chemical intensification treatment, but the composition before the composition and chemical intensification treatment in substrate deep layer portion is substantially It is identical.
As chemical enhanced condition, it is not particularly limited, can be according to for chemical enhanced glass types, required Chemical enhanced degree etc. selected.
As the fused salt for carrying out chemical intensification treatment, according to for chemical enhanced glass substrate select i.e. Can.It can enumerate for example：The alkali metal sulfates such as potassium nitrate, sodium sulphate, potassium sulfate, sodium chloride and potassium chloride and alkali metal chlorination Salt etc..These fused salts, which can be used alone, to use multiple combinations.
The heating-up temperature of fused salt is preferably more than 350 DEG C, more preferably more than 380 DEG C.Additionally, it is preferred that for less than 500 DEG C, More preferably less than 480 DEG C.
Heating-up temperature by setting fused salt can prevent from being difficult to because ion-exchange speed reduces as more than 350 DEG C Carry out chemical enhanced.In addition, by being set as less than 500 DEG C, decomposition, the deterioration of fused salt can be suppressed.
In addition, in order to assign sufficient compression, the time for making glass substrate be contacted with fused salt is preferably more than 1 hour, More preferably more than 2 hours.In addition, in the case of prolonged ion exchange, productivity ratio declines, and is made due to relaxation Value of compressive stress reduces, therefore preferably less than 24 hours, more preferably less than 20 hours.
Shape on transparent base is also not particularly limited, and can utilize variously-shaped transparent base.
The the second interarea 11B of transparent base 11 as described above with the first interarea 11A and corresponding thereto.Moreover, first The anti-dazzle processing to form desired concaveconvex shape is implemented on interarea 11A.Now, preferred the first interarea 11A surface roughness RMS is more than 0.05 μm and less than 0.25 μm, and the average length RSm of the first interarea 11A roughness curve key element is 10 μm Above and less than 40 μm.By surface roughness RMS and roughness curve key element that anti-soil film described later for the scope, can be made Average length RSm in desired scope.
Herein, surface roughness RMS refers to concavo-convex being averaged away from reference plane (being herein the substrate surface before surface treatment) Depth.It should be noted that also referred to as r.m.s. roughness, is also represented with Rq sometimes.In addition, roughness curve key element is averaged Length RSm refers in the roughness curve contained by the datum length that is obtained in reference plane, will appear from the concavo-convex base in a cycle Length obtained from length on quasi- face is carried out averagely.Surface roughness RMS (μm) and roughness curve key element average length RSm can be determined by the method based on method specified in JIS B 0601 (2001).
This is that the present inventor is waited to improve the durability progress of anti-soil film in the transparent base with anti-soil film The result studied and found, i.e. there is above-mentioned characteristic by making the first interarea 11A surface characteristic, in addition to anti-dazzle characteristic, Compared with the conventional transparent base with anti-soil film, especially the durability of anti-soil film improves.
Anti-soil film is formed in the first interarea side of transparent base, because anti-soil film makes carbon copies the surface configuration of transparent base, because And anti-soil film surface also has the surface roughness characteristics roughly the same with transparent base.
This means be more than 0.25 μm or RSm more than 40 μm with the RMS used in the past and implement the transparent of anti-dazzle processing Matrix phase ratio, by making the first interarea 11A of transparent base meet above-mentioned regulation, the micro concavo-convex of the first interarea of transparent base In, the spacing between recess diminishes, and the area increase of convex portion.Moreover, as described above, the surface of anti-soil film also has same table Face shape.
Finger etc. contact the transparent base with anti-soil film surface be anti-soil film in the case of, with the contact such as finger The convex portion area of anti-soil film increases compared with the conventional transparent base with anti-soil film.Therefore, finger etc. is applied to band anti-soil film The power of transparent base surface (anti-soil film) part disperseed, thus it is speculated that the pressure of anti-soil film is applied to thus, it is possible to reduce, can Suppress stripping, the abrasion of anti-soil film.
Speculate roughness curve key element average length RSm is smaller, i.e. the interval of recess is smaller, then with the contact surface of finger Product is bigger, and durability improves.But in order that RSm is very small, it is necessary to implement such as the etching process using photomask, from From the viewpoint of cost, as long as RSm is more than 10 μm, it becomes possible to preferably made.Therefore, it is excellent for the face of formation anti-soil film Choosing uses the transparent base for meeting above-mentioned RSm scopes.
In addition, in the case of the transparent base of RMS, RSm in above-mentioned number range, the spacing of recess is in appropriate scope It is interior, therefore the transparent base also with anti-dazzle characteristic can be obtained.
In addition, the first interarea 11A surface roughness RMS is preferably more than 0.08 μm and less than 0.20 μm, it is coarse to write music The average length RSm of line feature is preferably more than 15 μm and less than 35 μm.By meeting these parameters, the resistance to of anti-soil film can be made Long property further improves.
The anti-dazzle processing method that the transparent base with above-mentioned surface characteristic is made is not particularly limited, and can utilize to One interarea implements surface treatment and forms desired concavo-convex method.
Specifically, can enumerate：Implement the method for frosted processing for the first interarea of transparent base.Frosted handles example Such as can be by the way that the transparent base for being used as treated object be immersed in the mixed solution of hydrogen fluoride and ammonium fluoride so as to dipping Face carries out chemical surface treatment to carry out.
In addition, in addition to above-mentioned chemically treated method, can also will be crystallized using the method for for example so-called blasting treatment Silicon dioxide powder, carborundum powder etc. are with compressed air spraying to transparent base surface；Or the method for physical treatment, it will be attached with After the brush of ground silica, carborundum powder etc. is soaked with water, it is ground using the brush.
Particularly in the method for implementing to carry out the frosted processing of chemical surface treatment using reagent solutions such as hydrogen fluoride, no Micro-crack is easily produced on treated object surface, and does not allow to be also easy to produce mechanical strength reduction, therefore can be preferably as implementation The method of the surface treatment of transparent base uses.
After bumps are made in the above described manner, in order to repair surface configuration, can typically chemical etching be carried out to glass surface.By Mist degree can be adjusted to desired value by this by etch quantity, can remove the caused crackle in blasting treatment etc., additionally it is possible to Suppress dazzle.
As etching, it is preferable to use the transparent base as treated object is immersed in using hydrogen fluoride as main component Solution in method.As the composition beyond hydrogen fluoride, hydrochloric acid, nitric acid, citric acid etc. can be contained.By containing these things Matter, it can suppress that the phenomenon of evolution reaction locally occurs into alkali composition and the hydrogen fluoride reaction of glass, can make to be etched in Uniformly carried out in face.
For the second interarea 11B of transparent base, its characteristic is not particularly limited, and can also be machined so that it has The surface roughness RMS same with the first interarea and average length RSm of roughness curve key element.
Alternatively, it is also possible to which contact panel transparency electrode is made on the second interarea 11B of transparent base.So, pass through The transparency electrode of the contact panel composition integrated with the transparent base with anti-soil film is formed, can be realized further slim Lightweight.It should be noted that in this case, for the second interarea 11B, preferably without above-mentioned and the first interarea 11A Same anti-dazzle processing.
Moreover, in the first interarea 11A sides of transparent base 11 as shown in Figure 1 formed with anti-soil film 12.Anti-soil film 12 can be with It is made up of fluorine-containing organic silicon compound.
Here, fluorine-containing organic silicon compound is illustrated.As the fluorine-containing organic silicon chemical combination used in present embodiment Thing, it is not particularly limited to use as long as being to confer to soil resistance, water repellency, the fluorine-containing organic silicon compound can of oil repellent.
As such fluorine-containing organic silicon compound, can enumerate for example：With selected from by multi-fluoro polyether base, polyfluoro alkylene The fluorine-containing organic silicon compound of one or more of the group of base and Polyfluoroalkyl composition group.It should be noted that multi-fluoro polyether Base refer to have polyfluoro alkylidene replace bonding with etheric oxygen atom obtained from structure divalent group.
Have as this selected from one or more of the group being made up of multi-fluoro polyether base, polyfluoro alkylidene and Polyfluoroalkyl base The concrete example of the fluorine-containing organic silicon compound of group, it can enumerate by following logical formula (I)s~(V) compounds represented etc..
In formula, Rf be carbon number 1~16 straight chain Polyfluoroalkyl (as alkyl, such as：Methyl, ethyl, n-propyl, Isopropyl, normal-butyl etc.), X be hydrogen atom or carbon number 1~5 low alkyl group (such as：Methyl, ethyl, n-propyl, isopropyl Base, normal-butyl etc.), R1 be hydrolyzable group (such as amino, alkoxy etc.) or halogen atom (such as：Fluorine, chlorine, bromine, iodine Deng), integer, preferably 1~30 integers of the m for 1~50, integer, preferably 1~2 integers of the n for 0~2, p is 1~10 Integer, be preferably 1~8 integer.
CqF2q+1CH2CH2Si(NH2)3 (II)
Here, integer, preferably 2~20 integers of the q for more than 1.
As the compound represented by leading to formula (II), can enumerate for example：Trifluoro (1,1,2,2- tetrahydrochysenes) n-propyl silicon nitrogen Alkane (n-CF3CH2CH2Si(NH2)3), seven fluorine (1,1,2,2- tetrahydrochysenes) n-pentyl silazane (n-C3F7CH2CH2Si(NH2)3) etc..
Cq’F2q’+1CH2CH2Si(OCH3)3 (III)
Here, integer, preferably 1~20 integers of the q ' for more than 1.
As the compound represented by leading to formula (III), can enumerate for example：2- (perfluoro capryl) ethyl front three oxosilane (n-C8F17CH2CH2Si(OCH3)3) etc..
In formula (IV), Rf2Serve as reasons-(OC3F6)s-(OC2F4)t-(OCF2)u- (s, t, u be each independently 0~200 it is whole Number) represent divalent straight chain multi-fluoro polyether base, R2、R3Be each independently carbon number 1~8 monovalent hydrocarbon (such as：Methyl, Ethyl, n-propyl, isopropyl, normal-butyl etc.).X2、X3Independently be hydrolyzable group (such as amino, alkoxy, acyloxy, Alkenyloxy group, NCO etc.) or halogen atom (such as：Fluorine atom, chlorine atom, bromine atoms, iodine atom etc.), d, e are independently For 1~2 integer, c, f independently are the integer of 1~5 (being preferably 1~2), and a and b independently are 2 or 3.
R possessed by compound (IV)f2In, s+t+u is preferably 20~300, and more preferably 25~100.In addition, conduct R2、R3, more preferably methyl, ethyl, butyl.As by X2、X3The hydrolyzable groups of expression, more preferably carbon number 1~6 Alkoxy, particularly preferably methoxyl group, ethyoxyl.In addition, a and b are respectively preferably 3.
F-(CF2)v-(OC3F6)w-(OC2F4)y-(OCF2)z(CH2)hO(CH2)i-Si(X4)3-k(R4)k (V)
In formula (V), v is 1~3 integer, and w, y, z are each independently 0~200 integer, and h is 1 or 2, i are 2~20 Integer, X4For hydrolyzable groups, R4For the straight or branched alkyl of carbon number 1~22, k is 0~2 integer.W+y+z is excellent Elect 20~300, more preferably 25~100 as.In addition, i is preferably 2~10.X4The preferably alkoxy of carbon number 1~6, more Preferably methoxyl group, ethyoxyl.As R4, the preferably alkyl of carbon number 1~10.
In addition, have as commercially available in the group being made up of multi-fluoro polyether base, polyfluoro alkylidene and Polyfluoroalkyl The fluorine-containing organic silicon compound of more than one groups it is preferable to use KP-801 (trade name, chemical company of SHIN-ETSU HANTOTAI system), KY178 (trade name, chemical company of SHIN-ETSU HANTOTAI system), KY-130 (trade name, chemical company of SHIN-ETSU HANTOTAI system), KY-185 (trade name, SHIN-ETSU HANTOTAI Chemical company's system), OPTOOL (registration mark) DSX and OPTOOL AES (being trade name, big King Company's system) etc..
It should be noted that react and deteriorate to suppress the moisture in fluorine-containing organic silicon compound and air, It is typically mixed to preservation with equal solvent containing fluorous solvent, but when in the case of containing these solvents directly for film formation process, Durability of resulting film etc. is had undesirable effect sometimes.
Therefore, in the present embodiment, preferably solvent removing has been carried out in advance before container is heated using using heating The fluorine-containing organic silicon compound of processing or the fluorine-containing organic silicon compound without solvent dilution (being not added with solvent).Such as it is used as and contains Contained solvent strength, more preferably preferably 1 mole of below %, 0.2 mole of below % in fluorine organo-silicon compound solution.It is special Not solvent-laden fluorine-containing organic silicon compound is not preferably used.
It should be noted that as used solvent when preserving above-mentioned fluorine-containing organic silicon compound, can enumerate for example： Perflexane, hexafluoro meta-xylene (C6H4(CF3)2), hydrogen perfluoroalkyl polyether, HFE7200/7100 (trade name, Sumitomo 3M company systems, HFE7200 is by C4F9C2H5Expression, HFE7100 are by C4F9OCH3Represent) etc..
The processing of solvent (solvent) is removed from containing the fluorine-containing organic silicon compound solution containing fluorous solvent can for example lead to Cross and vacuum exhaust is carried out to the container for being put into fluorine-containing organic silicon compound solution and carried out.
On carrying out the time of vacuum exhaust, according to the exhaust capacity of exhaust line, vavuum pump etc., solution amount etc. and become Change, therefore do not limit, such as can be about more than 10 hours.
The film build method of the anti-soil film of present embodiment is not particularly limited, and preferably passes through vacuum evaporation using above-mentioned material Carry out film forming.
In addition, the removing processing of above-mentioned solvent can also be by importing to form anti-soil film fluorine-containing organic silicon compound solution Film formation device heating container, then before heating at room temperature to heating container in carry out vacuum exhaust and carry out.In addition, Evaporator etc. can also be advanced with before heating container is imported remove solvent.
But as described above, solvent is few or not solvent-laden fluorine-containing organic silicon compound, with the situation containing solvent Compare, easily due to being deteriorated with atmosphere.
Therefore, the preservation container of the fluorine-containing organic silicon compound of solvent few (or without solvent) is preferably used container It is middle with inert gas replacements such as nitrogen and it is closed after container, and shorten when being operated and be exposed to air and atmosphere Time.
Specifically, preferably by preserve container Kaifeng after fluorine-containing organic silicon compound is imported immediately to be formed anti-soil film into The heating container of film device.Moreover, preferably making to turn into heating container vacuum after importing or with indifferent gas such as nitrogen, rare gas Body enters line replacement, thus removes air (air) contained in heating container.In order in the case of not with atmosphere It is directed into from container (storage container) is preserved in the heating container of this manufacture device, such as preferably by storage container and heating container Connected by the pipe arrangement with valve.
Moreover, after fluorine-containing organic silicon compound is imported into heating container, vacuum is formed preferably in container or uses indifferent gas After body displacement, the heating for film forming is immediately begun to.
As the film build method of anti-soil film, had describing in description of the present embodiment using solution or the fluorine-containing of stoste The example of organic silicon compound, but not limited to this.As other methods, such as：It is referred to as evaporation using commercially available and (is used as one by the use of particle Example, キ ャ ノ Application オ プ ト ロ Application company system サ ー Off Network リ ア) method, the evaporation particle is a certain amount of by making in advance Fluorine-containing organic silicon compound is infiltrated up in porous metals (such as tin or copper) or fibrous metal (such as stainless steel) and obtained. In this case, can also be simply formed according to the particle of evaporation coating device capacity, the amount of required thickness as vapor deposition source Anti-soil film.
As noted previously, as anti-soil film directly makes carbon copies the surface configuration of transparent base, thus its surface characteristic and transparent base The surface roughness RMS of body and the average length RSm of roughness curve key element are identical.Therefore, its surface roughness RMS is 0.05 More than μm and less than 0.25 μm, and the average length RSm of roughness curve key element is more than 10 μm and less than 40 μm.It is in addition, special It is not that surface roughness RMS is more preferably more than 0.08 μm and less than 0.20 μm, the average length RSm of roughness curve key element More preferably more than 15 μm and less than 35 μm.
In addition, in order to improve the adhesiveness of transparent base and anti-soil film, can be inserted between transparent base and anti-soil film Adhesion layer.In the case where inserting adhesion layer, it is formed in advance on the first interarea of transparent base before anti-soil film is formed .As adhesion layer, preferably using silicon oxide film.Be more than 2nm and below 50nm as thickness, preferably more than 5nm and Below 20nm.
It is illustrated above for each component of the transparent base with anti-soil film of present embodiment, present embodiment The mist degree of transparent base with anti-soil film is preferably more than 2% and less than 30%.Because mist degree is if more than 2%, with The substrate that anti-dazzle processing is not carried out is compared, and can significantly suppress the mapping (reflecting り こ body) of light through visually confirmation；If greater than 30%, then cause light diffusing reflection, in the The lid component as display device or the substrate integrated with contact panel in use, can drop The visuality of the display of low display device.In addition, the mist degree of the transparent base with anti-soil film of present embodiment is preferably 15% Above and less than 27%.
Have shown：By mist degree within the above range, the transparent base with anti-soil film of present embodiment has sufficient Anti-dazzle characteristic, it can be utilized more preferably as the The lid component of display device etc. or the substrate integrated with contact panel.
According to the transparent base with anti-soil film of present embodiment discussed above, can obtain same with anti-dazzle characteristic When improve anti-soil film durability the transparent base with anti-soil film.
[the 2nd embodiment]
In the present embodiment, illustrated for being additionally provided with the composition of low-reflection film in the 1st embodiment.For Other compositions, due to as illustrated in the 1st embodiment, therefore omit herein.
Low-reflection film can suppress the reflection in the light on the transparent base surface with anti-soil film, therefore can make anti-dazzle characteristic Further improve.For example, the The lid component as display device in use, can suppress the mapping of the light of surrounding, further improves The visuality of the display of display device.
The material of low-reflection film is not particularly limited, as long as the material of reflection can be suppressed, it is possible to utilize various materials Material.For example, as low-reflection film, can be formed composition obtained from high refractive index layer and low-refraction layer stackup.
High refractive index layer and low-index layer can be the form for each including 1 layer, or each self-contained more than 2 layers Composition.When each self-contained more than 2 layers of high refractive index layer and low-index layer, preferably high refractive index layer and low-index layer Alternately laminated form.
In order to obtain sufficient antireflection property, low-reflection film is preferably the layered product for being laminated with multiple films (layer).For example, The preferred total of the layered product is laminated with more than 2 layers and less than 6 layers of film, is more preferably laminated with the film of more than 2 layers and less than 4 layers. Layered product herein is preferably high by layered product obtained from high refractive index layer and low-refraction layer stackup, and preferably as described above The total of the number of plies of index layer and low-index layer is within the above range.
High refractive index layer, the material of low-index layer are not particularly limited, it may be considered that required antireflection degree, life Yield etc. is selected.As the material for forming high refractive index layer, such as can be preferably by selected from niobium oxide (Nb2O5), oxidation Titanium (TiO2), zirconium oxide (ZrO2), silicon nitride (SiN) and tantalum oxide (Ta2O5) more than one.As composition low-index layer Material, can be preferably by silica (SiO2)。
As high refractive index layer, consider from productivity ratio, refractive index degree, particularly preferably utilize niobium oxide.Therefore, it is above-mentioned low Reflectance coating is more preferably the layered product of niobium oxide layer and silicon oxide layer.
In the transparent base with anti-soil film of present embodiment, for setting the position of low-reflection film to have no special limit It is fixed, it can be arranged on the first interarea 11A and/or the second interarea 11B of transparent base.Particularly preferably it is arranged on transparent base On first interarea 11A.Such as shown in Fig. 2, more preferably formed on the first interarea 11A of transparent base 11 surface (from the first master Surface side rise) on be sequentially laminated with low-reflection film 13, the composition of fluorine-containing organic silicon compound overlay film 12.
As described above by being formed low-reflection film 13, fluorine-containing organic silicon are laminated with the first interarea 11A of transparent base The composition of compound overlay film (anti-soil film) 12, it also can prevent low-reflection film 13 from peeling off and improve durability, therefore preferably.
In addition, insertion improve anti-soil film durability adhesion layer in the case of, preferably put it into low-reflection film with Between anti-soil film.In this case, silicon oxide film is also the material preferably used, as shown in above-mentioned example in low-reflection film In the case that the superiors are also silica, low reflectivity and the effect of adhesion layer can be realized simultaneously, therefore be preferably to form.
In fig. 2, low-reflection film 13 is formed as being laminated with 2 layer 131,132 composition, but is not limited to the form, Multiple layers of composition can be formed as further being laminated with as described above.
In addition, for the transparent base with anti-soil film of present embodiment, based on phase illustrated in the 1st embodiment Same reason, mist degree are preferably also more than 2% and less than 30%, more preferably more than 15% and less than 27%.
More than, in the present embodiment, it is illustrated, leads to for the transparent base with anti-soil film with low-reflection film Cross with this composition, can further improve anti-dazzle characteristic.Therefore, can be more preferably in the lid arrangement or and touch-control of display device Used in the purposes of the special requirement anti-dazzle characteristic such as substrate of panel integration.
Embodiment
It is exemplified below specific embodiment to illustrate, but the present invention is not limited to these embodiments.Need what is illustrated It is that 1~example of example 4 is embodiment, 5~example of example 7 is comparative example.
(1) evaluation method
The evaluating characteristics of the transparent base with anti-soil film for being obtained in following 1~example of example 7 are described as follows.
(surface shape measuring)
For the surface configuration of the anti-soil film of the sample after the anti-soil film film forming that is used in 1~example of example 7, laser capture microdissection is used Mirror (Ji Ensi (キ ー エ Application ス) company system, trade name：VK-9700 face profile) is determined with 50 times of multiplying power.Then, from To face profile surface roughness RMS and the average length RSm of roughness curve key element are obtained based on JIS B0601 (2001) Value.
The anti-soil film of film forming, low-reflection film are relative to the very thin film of the thickness of transparent base, therefore surface in each example Concaveconvex structure substantially directly make carbon copies transparent base surface configuration.Therefore, for transparent base (formed with anti-soil film side Face) surface configuration, it is believed that and identical.
(mist degree measure)
In embodiment, comparative example, the measure of transmittance haze is carried out for the sample after formation anti-soil film.Surveyed for mist degree It is fixed, use haze meter (ス ガ testing machines Co. Ltd. system, model：HZ-V3) carry out.
(friction durability (wearability) experiment)
For the sample after anti-soil film film forming in 1~example of example 7, rubbed for the anti-soil film of the sample with following step Endurancing.
Friction test is carried out with following step firstly, for the anti-soil film of example 1~7.
Steel wool #0000 is installed for the surface of 10mm × 10mm planar metal pressure head in bottom surface friction sample is made Friction head.
Then, using above-mentioned friction head, formula (Daiei science essence device company system, model are connected with plane abrasion testing machine 3：PA- 300A) carry out friction test.Specifically, installed first in a manner of the bottom surface of above-mentioned pressure head contacts with the antifouling film surface of sample On abrasion testing machine, and load weight and cause to be 1000g to the load of friction head, in average speed 6400mm/ minutes and list Reciprocatingly slided under conditions of journey 40mm.Rubbing number is counted as by reciprocal 1 time 1 time, and in a manner of Rubbing number is 1000 times Tested.
Then, the measure of water contact angle is carried out with following step for anti-soil film.
The measure of the water contact angle of anti-soil film is by using automatic contact angle meter (consonance interface science company system, model： DM-501), dripped on anti-soil film and the μ L of pure water 1 and determine its contact angle and carry out.During measure, for each sample in anti-soil film table It is measured at the 10 of face, and is averaged value as the water contact angle after the endurancing of the sample.
Now, water contact angle is evaluated as qualified for more than 90 °, and water contact angle is evaluated as unqualified for less than 90 °.
(2) experimental procedure
[example 1]
The transparent base with anti-soil film is manufactured by following steps.
In this example, as transparent base, glass substrate (the Asahi Glass strain formula meeting of chemical intensification treatment is implemented using use Society's system, trade name：" Dragontrail " (registration mark)) and defined frosted has been carried out to the first interarea of the glass substrate Glass substrate obtained from processing (is designated as transparent base A) below.
Then, anti-soil film is formed with following step on transparent base A the first interarea.
First, by fluorine-containing organic silicon compound (KCC of SHIN-ETSU HANTOTAI system, trade name：KY-185 heating container) is imported It is interior to be used as deposition material.Then, by heating container in using vavuum pump degassing more than 10 hours it is molten in solution to remove Agent, so as to which fluorine-containing organic silicon compound overlay film formation composition be made.
Next, 270 DEG C will be heated to the heating container of composition equipped with above-mentioned fluorine-containing organic silicon compound film formation. After reaching 270 DEG C, its state is kept for 10 minutes untill temperature stabilization.
Then, to the transparent base A that is arranged in vacuum chamber the first interarea (face handled through frosted), from equipped with upper State the nozzle supply fluorine-containing organic silicon compound film shape of the heating container connection of fluorine-containing organic silicon compound film formation composition Into with composition, and carry out film forming.
During film forming, film forming is carried out while the crystal oscillator monitor by being arranged in vacuum chamber determines thickness, Until the thickness of the fluorine-containing organic silicon compound film formed on transparent base A reaches 10nm.
Stop at the time of fluorine-containing organic silicon compound film reaches 10nm from nozzle base feed, and taken out from vacuum chamber Transparent base A formed with fluorine-containing organic silicon compound film.
The transparent base A that the formation of taking-up has fluorine-containing organic silicon compound film is arranged on hot plate in a manner of film surface is upward On, and at 150 DEG C be heat-treated within 60 minutes in an atmosphere.
For obtained sample in the above described manner, above-mentioned surface shape measuring, mist degree measure and friction durability examination are carried out Test.Show the result in table 1.
[example 2]
As transparent base, using using glass substrate (Asahi Glass Co., Ltd's system, the business for implementing chemical intensification treatment The name of an article：" Dragontrail " (registration mark)) and carried out the transparent base of frosted processing to the first interarea of the glass substrate B, in addition, anti-soil film is formed on transparent base B the first interarea in a manner of same as Example 1.Prevent for obtained band The transparent base of dirty film, is evaluated in a manner of same as Example 1.Show the result in table 1.
[example 3]
As transparent base, using using glass substrate (Asahi Glass Co., Ltd's system, the business for implementing chemical intensification treatment The name of an article：" Dragontrail " (registration mark)) and carried out the transparent base of frosted processing to the first interarea of the glass substrate C, in addition, anti-soil film is formed on transparent base C the first interarea in a manner of same as Example 1.Prevent for obtained band The transparent base of dirty film is evaluated in a manner of same as Example 1.Show the result in table 1.
[example 4]
Low-reflection film is formed in the following manner on transparent base A.
First, niobium oxide target (AGC is used while the 10 volume % mixed gas of oxygen is mixed with importing argon gas Ceramic Corporation's system, trade name NBO targets) in pressure 0.3Pa, frequency 20kHz, power density 3.8W/cm2, reverse impulse width 5 it is micro- Pulsed sputter is carried out under conditions of second, so as to which form thickness 13nm on transparent base A the first interarea includes niobium oxide (niobia) high refractive index layer.
Next, using silicon target in pressure while the 40 volume % mixed gas of oxygen is mixed with importing argon gas 0.3Pa, frequency 20kHz, power density 3.8W/cm2, under conditions of the microsecond of reverse impulse width 5, in the microsecond of pulse width 5 Under the conditions of carry out pulsed sputter, so as to form the low comprising silica (silica) of thickness 30nm on above-mentioned high refractive index layer Index layer.
Next, use niobium oxide target while the 10 volume % mixed gas of oxygen is mixed with importing argon gas (AGC Ceramic Corporations system, trade name NBO targets) is in pressure 0.3Pa, frequency 20kHz, power density 3.8W/cm2, reverse impulse it is wide Spend under conditions of 5 microseconds and carry out pulsed sputter, so as to which form thickness 110nm on above-mentioned low-index layer includes niobium oxide (niobia) high refractive index layer.
Next, using silicon target in pressure while the 40 volume % mixed gas of oxygen is mixed with importing argon gas 0.3Pa, frequency 20kHz, power density 3.8W/cm2, under conditions of the microsecond of reverse impulse width 5, in the microsecond of pulse width 5 Under the conditions of carry out pulsed sputter and form the thickness 90nm low-index layer for including silica (silica).
The low reflection that total is laminated with 4 layers of niobium oxide (niobia) and silica (silica) is formd in the above described manner Film.
Next, anti-soil film is formed on low-reflection film in a manner of same as Example 1.
For the obtained transparent base with anti-soil film, evaluated in a manner of same as Example 1.Show the result in table 1.
[example 5]
As transparent base, using using glass substrate (Asahi Glass Co., Ltd's system, the business for implementing chemical intensification treatment The name of an article：" Dragontrail " (registration mark)) and carried out the transparent base of frosted processing to the first interarea of the glass substrate D, in addition, anti-soil film is formed on transparent base D the first interarea in a manner of same as Example 1.Prevent for obtained band The transparent base of dirty film is evaluated in a manner of same as Example 1.Show the result in table 1.
[example 6]
As transparent base, using using glass substrate (Asahi Glass Co., Ltd's system, the business for implementing chemical intensification treatment The name of an article：" Dragontrail " (registration mark)) and carried out the transparent base of frosted processing to the first interarea of the glass substrate E, in addition, anti-soil film is formed on transparent base E the first interarea in a manner of same as Example 1.Prevent for obtained band The transparent base of dirty film is evaluated in a manner of same as Example 1.Show the result in table 1.
[example 7]
As transparent base, using transparent base D same as Example 5, in addition, formed in a manner of same as Example 4 Low-reflection film and anti-soil film, evaluated for the obtained transparent base with anti-soil film in a manner of same as Example 1.By result It is shown in table 1.
[table 1]
It can be seen from the result shown in table 1, on meet present invention provide that example 1~4, friction endurancing reclaimed water Contact angle is more than 90 °, and on the other hand, on example 5~7, water contact angle is less than 80 °.
Anti-soil film has water repellency, and the situation that water contact angle as described above diminishes represents that anti-soil film is peeled off, worn.Therefore, On example 5~7, it is known that anti-soil film is peeled off, abrasion.
By these results it has been confirmed that on meet present invention provide that example 1~4, compared with the example 5~7 of comparative example, prevent The durability of dirty film becomes very high.
In addition, on example 1~4, it can also confirm that it has appropriate anti-dazzle characteristic according to its haze value.
More than, the transparent base with anti-soil film is illustrated using embodiment and embodiment etc., but it is of the invention It is not limited to the above-described embodiment and examples etc..Can be with the range of the idea of the invention recorded in detail in the claims Carry out various modifications, change.
This application claims the Japanese Patent Application 2013-015968 to be filed an application based on January 30th, 2013 to the Japanese Patent Room Number priority, and the full content of Japanese Patent Application 2013-015968 is quoted in this international application.
Reference
11 transparent bases
12 anti-soil films
13 low-reflection films

Claims (9)

1. a kind of glass basis with anti-soil film, it has：
Glass basis, the glass basis have the first interarea and second interarea relative with first interarea, and described The surface of first interarea implements anti-dazzle processing；With
Fluorine-containing organic silicon compound overlay film, the fluorine-containing organic silicon compound overlay film are be arranged on the glass basis described The anti-soil film of one interarea side；
The surface roughness RMS on the surface for implementing anti-dazzle processing is more than 0.05 μm and less than 0.25 μm, and roughness The average length RSm of curve element is more than 10 μm and less than 40 μm；
The surface roughness RMS of the anti-soil film is more than 0.05 μm and less than 0.25 μm, and roughness curve key element is averaged Length RSm is more than 10 μm and less than 40 μm.
2. the glass basis with anti-soil film as claimed in claim 1, wherein, the mist degree of the glass basis with anti-soil film is More than 2% and less than 30%.
3. the glass basis with anti-soil film as claimed in claim 1 or 2, wherein, in first master of the glass basis Low-reflection film, fluorine-containing organic silicon compound overlay film are sequentially laminated with the surface in face.
4. the glass basis with anti-soil film as claimed in claim 3, wherein, the low-reflection film is niobium oxide layer and silica The layered product of layer.
5. the glass basis with anti-soil film as claimed in claim 4, wherein, the low-reflection film obtains to be laminated multiple films Layered product, amount in the layered product and be laminated with more than 2 layers and less than 6 layers of film.
6. the glass basis with anti-soil film as claimed in claim 1, wherein, the surface roughness RMS of first interarea is More than 0.08 μm and less than 0.20 μm.
7. the glass basis with anti-soil film as claimed in claim 3, wherein, the surface roughness RMS of first interarea is More than 0.08 μm and less than 0.20 μm.
8. the glass basis with anti-soil film as claimed in claim 1, wherein, the roughness curve key element of first interarea Average length RSm is more than 15 μm and less than 35 μm.
9. the glass basis with anti-soil film as claimed in claim 3, wherein, the roughness curve key element of first interarea Average length RSm is more than 15 μm and less than 35 μm.
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DE112014000613B4 (en) 2019-05-29
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KR20170137223A (en) 2017-12-12
TW201434775A (en) 2014-09-16

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