CN108129032A - Transparent base with anti-soil film - Google Patents

Transparent base with anti-soil film Download PDF

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Publication number
CN108129032A
CN108129032A CN201711338071.2A CN201711338071A CN108129032A CN 108129032 A CN108129032 A CN 108129032A CN 201711338071 A CN201711338071 A CN 201711338071A CN 108129032 A CN108129032 A CN 108129032A
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Prior art keywords
transparent base
film
soil film
interarea
soil
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Granted
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CN201711338071.2A
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CN108129032B (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
    • C03C17/34—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
    • 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
    • C03C17/28—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
    • 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)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Wood Science & Technology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Liquid Crystal (AREA)

Abstract

The present invention provides a kind of transparent base with anti-soil film, has：Transparent base, the transparent base has the first interarea and second interarea opposite 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 0.05 μm or more and 0.25 μm hereinafter, and the average length RSm of roughness curve element is 10 μm or more and less than 40 μm.

Description

Transparent base with anti-soil film
It is on January 22nd, 2014, international application no PCT/JP2014/051291, China's application the applying date that the application, which is, Number for 201480006778.1 patent application divisional application.
Technical field
The present invention relates to the transparent bases with anti-soil film.
Background technology
In recent years, mostly using various display devices such as liquid crystal displays especially in mancarried device, vehicle-mounted equipment. 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 touch panel with transparent 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 When touching, grease etc. is easily adhered on transparent base surface.Moreover, when grease is when attachments, visuality can be influenced, therefore Use the transparent base that antifouling process is implemented on the surface of transparent base.
As disclosing a kind of water repellency in the transparent base for implementing antifouling process on the surface, such as patent document 1 Glass 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, since 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 shape of glass substrate is made it is predetermined The method (such as patent document 2) of shape.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 07-126041 bulletins
Patent document 2：Japanese Unexamined Patent Publication 11-171594 bulletins
Invention content
Problem to be solved by the invention
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 touch panel The integrated protective glass of transparent electrode in use, due to almost without anti-dazzle characteristic, exist the light around mapping so as to 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 the The lid component touched by human hand while upper frequency is possible to as display device or With the integrated substrate of touch panel in use, durability is insufficient.
In view of problem possessed by the above-mentioned prior art, same with anti-dazzle characteristic the object of the present invention is to provide one kind When improve anti-soil film durability the transparent base with anti-soil film.
The means used to solve the problem
To solve the above-mentioned problems, the present invention provides a kind of transparent base with anti-soil film, has：
Transparent base, the transparent base have the first interarea and second interarea opposite 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 0.05 μm or more and 0.25 μm hereinafter, and roughness curve element Average length RSm is 10 μm or more and less than 40 μm.
Invention effect
In the present invention, be capable of providing a kind of durability for improving anti-soil film simultaneously with anti-dazzle characteristic with anti-soil film Transparent base.
Description of the drawings
Fig. 1 is the definition graph of the composition of the transparent base with anti-soil film of the 1st embodiment of the present invention.
Fig. 2 is the definition graph of the composition of the transparent base with anti-soil film of the 2nd embodiment of the present invention.
Specific embodiment
The mode for being used to implement the present invention is described with reference to the accompanying drawings, but the present invention is not limited to following implementations below Mode can impose various modifications and displacement 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 opposite 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 characterized in that：The surface roughness RMS of above-mentioned anti-soil film for 0.05 μm with It is upper and 0.25 μm hereinafter, and the average length RSm of roughness curve element is 10 μm or more 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 has and is 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 a variety of 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 type 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 is, it is preferable to use soda-lime glass.
Transparent base 11 be glass substrate in the case of, from the viewpoint of the intensity of transparent base in itself, it is preferable to 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, by the glass containing sodium ion with the fused salt containing potassium ion into Row processing, it is possible thereby to carry out chemical strengthening.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 the condition of chemical strengthening, it is not particularly limited, it can be according to the glass types, required for chemical strengthening Chemical strengthening degree etc. selected.
As for carrying out the fused salt of chemical intensification treatment, according to the glass substrate for chemical strengthening select i.e. It 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 temperature of fused salt is preferably 350 DEG C or more, more preferably 380 DEG C or more.Additionally, it is preferred that for 500 DEG C hereinafter, More preferably less than 480 DEG C.
Heating temperature by setting fused salt can prevent from being difficult to since ion-exchange speed reduces as 350 DEG C or more Carry out chemical strengthening.In addition, by being set as 500 DEG C hereinafter, the decomposition of fused salt, deterioration can be inhibited.
In addition, in order to assign sufficient compression, it is preferably 1 hour or more to make the time that glass substrate is contacted with fused salt, More preferably 2 hours or more.In addition, in the case of prolonged ion exchange, productivity declines, and is made due to relaxation Value of compressive stress reduce, therefore preferably 24 hours hereinafter, more preferably less than 20 hours.
Shape about 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.At this point, the it is preferred that surface roughness of the first interarea 11A RMS is 0.05 μm or more and 0.25 μm hereinafter, and the average length RSm of the roughness curve element of the first interarea 11A is 10 μm Above and less than 40 μm.By the way that for the range, the surface roughness RMS of aftermentioned anti-soil film and roughness curve element can be made Average length RSm in desired range.
Herein, surface roughness RMS refers to concave-convex being averaged away from datum level (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 sometimes with Rq.In addition, roughness curve element is averaged Length RSm refers in the roughness curve contained by the datum length obtained on datum level the concave-convex base in a period will occur Length obtained from length on quasi- face carries out averagely.The average length of surface roughness RMS (μm) and roughness curve element RSm can be measured by being based on the method for method specified in JIS B 0601 (2001).
This is that the present inventor waits the durability for the raising anti-soil film in the transparent base with anti-soil film to carry out The result studied and found, that is, there is above-mentioned characteristic by the surface characteristic for making the first interarea 11A, other than anti-dazzle characteristic, Compared with the previous 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, since anti-soil film makes carbon copies the surface shape of transparent base, because And antifouling film surface also has the surface roughness characteristics roughly the same with transparent base.
It is more than 40 μm this means that being more than 0.25 μm or RSm with the RMS used in the past and implements the transparent of anti-dazzle processing Matrix is compared, and meets above-mentioned regulation, the micro concavo-convex of the first interarea of transparent base by the first interarea 11A for making transparent base In, the spacing between recess portion becomes smaller, and the area increase of protrusion.Moreover, as described above, the surface of anti-soil film also has same table Face shape.
In the case where finger etc. contacts surface, that is, anti-soil film of the transparent base with anti-soil film, with the contacts such as finger The protrusion area of anti-soil film increases compared with the previous 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, can thus, it is possible to reduce to be applied to the pressure of anti-soil film Inhibit stripping, the abrasion of anti-soil film.
Speculate roughness curve element average length RSm is smaller, i.e. the interval of recess portion is smaller, then with the contact surface of finger Product is bigger, and durability improves.But in order to make RSm very small, need to implement such as the etching process using photomask, from From the perspective of cost, as long as RSm is 10 μm or more, it will be able 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 ranges.
In addition, in the case of the transparent base of RMS, RSm in above-mentioned numberical range, the spacing of recess portion is in appropriate range It is interior, therefore the transparent base also with anti-dazzle characteristic can be obtained.
In addition, the surface roughness RMS of the first interarea 11A is preferably 0.08 μm or more and 0.20 μm hereinafter, coarse write music The average length RSm of line feature is preferably 15 μm or more 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 The method that one interarea implements surface treatment and forms desired bumps.
Specifically, it can enumerate：The method of frosted processing is implemented for the first interarea of transparent base.Frosted handles example It 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 on 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 generated 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 modify surface shape, can generally 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 crackle generated in blasting treatment etc., additionally it is possible to Inhibit dazzle.
As etching, it is preferable to use the transparent base for being used as treated object is immersed in using hydrogen fluoride as main component Solution in method.As the ingredient other than hydrogen fluoride, hydrochloric acid, nitric acid, citric acid etc. can be contained.By containing these objects Matter can inhibit the phenomenon that evolution reaction locally occurs into alkali composition and the hydrogen fluoride reaction of glass, can make to be etched in It is uniformly carried out in face.
For the second interarea 11B of transparent base, characteristic is not particularly limited, and can also be machined so that it has The average length RSm of surface roughness RMS same with the first interarea and roughness curve element.
Alternatively, it is also possible to which touch panel transparent electrode is made on the second interarea 11B of transparent base.In this way, pass through The transparent electrode of touch panel and the integrated composition of the transparent base with anti-soil film are 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, the first interarea 11A sides in transparent base 11 are formed with anti-soil film 12 as shown in Figure 1.Anti-soil film 12 can be with It is made 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 Object, as long as be to confer to soil resistance, water repellency, oil repellent fluorine-containing organic silicon compound be not particularly limited to use.
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.
There is one or more of the group for being selected from and being made of multi-fluoro polyether base, polyfluoro alkylidene and Polyfluoroalkyl base as this The concrete example of the fluorine-containing organic silicon compound of group, can enumerate by the following general formula (I)~(V) compounds represented etc..
In formula, Rf be carbon atom number 1~16 straight chain Polyfluoroalkyl (as alkyl, such as：Methyl, ethyl, n-propyl, Isopropyl, normal-butyl etc.), X be hydrogen atom or carbon atom number 1~5 low alkyl group (such as：Methyl, ethyl, n-propyl, isopropyl Base, normal-butyl etc.), R1 for 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, 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..
Cg′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 atom 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, isocyanate group 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 (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 atom number 1~6 Alkoxy, particularly preferably methoxyl group, ethyoxyl.In addition, a and b are respectively preferably 3.
F-(CF2)v-(OC3F6)w-(0C2F4)y-(OCF2),(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 linear chain or branch chain alkyl of carbon atom number 1~22, k is 0~2 integer.W+y+z is excellent It is selected as 20~300, more preferably 25~100.In addition, i is preferably 2~10.X4The preferably alkoxy of carbon atom number 1~6, more Preferably methoxyl group, ethyoxyl.As R4, the preferably alkyl of carbon atom number 1~10.
In addition, have in the group being made of multi-fluoro polyether base, polyfluoro alkylidene and Polyfluoroalkyl as commercially available 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 (registered trademark) DSX and OPTOOL AES (being trade name, big King Company's system) etc..
It should be noted that deteriorated in order to which fluorine-containing organic silicon compound is inhibited to react with the moisture in air, It is generally mixed to preservation with fluoride solvent equal solvent, but when in the case of containing these solvents directly for film formation process, Harmful effect is caused to durability of obtained film etc. sometimes.
Therefore, in the present embodiment, it is preferable to use having carried out solvent removing in advance before container is heated 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 in fluorine organo-silicon compound solution, preferably 1 mole of % is hereinafter, more preferably 0.2 mole of below %.It is special It is preferable to use not solvent-laden fluorine-containing organic silicon compounds.
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 corporations, HFE7200 is by C4F9C2H5It represents, HFE7100 is by C4F9OCH3Represent) etc..
The processing of solvent (solvent) is removed from the fluorine-containing organic silicon compound solution containing fluoride solvent can for example lead to It crosses and the container for being put into fluorine-containing organic silicon compound solution is vacuum-evacuated and is carried out.
About the time being vacuum-evacuated, according to the exhaust capacity of exhaust line, vacuum pump etc., solution amount etc. and become Change, therefore do not limit, such as can be about 10 hours or more.
The film build method of the anti-soil film of present embodiment is not particularly limited, it is preferable to use above-mentioned material passes through vacuum evaporation It forms a film.
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 at room temperature to being vacuum-evacuated and being carried out in heating container before heating.In addition, Evaporator etc. can also be advanced with before heating container is imported remove solvent.
But as described above, solvent content is few or not solvent-laden fluorine-containing organic silicon compound, with the situation containing solvent It compares, easily due to being deteriorated with atmosphere.
Therefore, it is preferable to use by container for the preservation container of the fluorine-containing organic silicon compound of solvent content few (or without solvent) Middle container with inert gas replacements such as nitrogen and after closed, and shorten when being operated and be exposed to air and atmosphere Time.
Specifically, it is preferable that 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 become in heating container vacuum after importing or with indifferent gas such as nitrogen, rare gas Thus body removes air (air) contained in heating container into line replacement.In order in the case of not with atmosphere It is directed into the heating container of this manufacturing device from container (storage container) is preserved, such as preferably by storage container and heating container It is connected by the piping with valve.
Moreover, after fluorine-containing organic silicon compound is imported 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 known as vapor deposition by the use of particle (as one using commercially available Example, キ ャ ノ Application オ プ ト ロ Application corporation サ ー Off Network リ ア) method, the vapor deposition 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 obtains. In this case, it can also be simply formed according to the particle of evaporation coating device capacity, the amount of required film thickness as evaporation source Anti-soil film.
As noted previously, as anti-soil film directly makes carbon copies the surface shape of transparent base, thus its surface characteristic and transparent base The surface roughness RMS of body and the average length RSm of roughness curve element are identical.Therefore, surface roughness RMS is 0.05 μm or more and 0.25 μm hereinafter, and roughness curve element average length RSm be 10 μm or more and less than 40 μm.It is in addition, special It is not that surface roughness RMS is more preferably 0.08 μm or more and 0.20 μm hereinafter, the average length RSm of roughness curve element More preferably 15 μm or more 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 being inserted into adhesion layer, it is formed in advance on the first interarea of transparent base before anti-soil film is formed .As adhesion layer, it is preferable to use silicon oxide film.As film thickness, be more than 2nm and 50nm hereinafter, preferably more than 5nm and Below 20nm.
Each component of the transparent base with anti-soil film of present embodiment is illustrated above, present embodiment The mist degree of transparent base with anti-soil film is preferably more than 2% and less than 30%.This is because mist degree is if it is more than 2%, with The substrate that anti-dazzle processing is not carried out is compared, and can significantly inhibit the mapping (reflecting り こ body) of light through visual confirmation；If greater than 30%, then lead to light diffusing reflection, the The lid component as display device or with the integrated substrate of touch 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%.
It has shown：By mist degree within the above range, the transparent base with anti-soil film of present embodiment has sufficient Anti-dazzle characteristic can be utilized more preferably as the The lid component of display device etc. or substrate integrated with touch 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, it is 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, omitting herein.
Low-reflection film can inhibit the reflection in the light on the transparent base surface with anti-soil film, therefore can make anti-dazzle characteristic It further improves.For example, the The lid component as display device is further improved in use, can inhibit the mapping of the light of surrounding 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 inhibited, 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 to respectively contain 1 layer of form, or respectively contain 2 layers or more Composition.When respectively containing 2 layers or more of high refractive index layer and low-index layer, preferably high refractive index layer and low-index layer Alternately stacked form.
Sufficient antireflection property in order to obtain, low-reflection film are preferably the laminated body for being laminated with multiple films (layer).For example, The preferred total of the laminated body is laminated with 2 layers or more and less than 6 layers of film, is more preferably laminated with the film of 2 layers or more and less than 4 layers. Laminated body herein is as described above preferably by laminated body obtained from high refractive index layer and low-refraction layer stackup, and preferred height The total of the number of plies of index layer and low-index layer is within the above range.
High refractive index layer, low-index layer material be 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, refractive index degree, particularly preferably utilize niobium oxide.Therefore, it is above-mentioned low Reflectance coating is more preferably the laminated body of niobium oxide layer and silicon oxide layer.
In the transparent base with anti-soil film of present embodiment, special limit is had no for the position for setting low-reflection film 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, the surface of the first interarea 11A of transparent base 11 is more preferably formed in (from the first master Rise surface side) on be sequentially laminated with the composition of low-reflection film 13, fluorine-containing organic silicon compound overlay film 12.
Low-reflection film 13, fluorine-containing organic silicon are laminated with as described above by being formed on the first interarea 11A of transparent base The composition of compound overlay film (anti-soil film) 12 also can prevent low-reflection film 13 from removing and improve durability, therefore preferably.
In addition, be inserted into 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 be also it is preferable to use material, as shown in above-mentioned example in low-reflection film Top layer is also in the case of silica, to can be achieved at the same time low reflectivity and the effect of adhesion layer, being therefore preferred composition.
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, It can be formed as further being laminated with multiple layers of composition as described above.
In addition, for the transparent base with anti-soil film of present embodiment, based on the phase illustrated in the 1st embodiment Same reason, mist degree are preferably also more than 2% and 30% hereinafter, more preferably more than 15% and less than 27%.
More than, in the present embodiment, the transparent base with anti-soil film with low-reflection film is illustrated, is led to It crosses with this composition, anti-dazzle characteristic can be further improved.It therefore, can be more preferably in the lid arrangement of display device or and touch-control It is used in the purposes of the special requirement anti-dazzle characteristic such as integrated substrate of panel.
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 obtained in following 1~example of example 7 are described as follows.
(surface shape measuring)
The surface shape of the anti-soil film of sample after forming a film for the anti-soil film used in 1~example of example 7, uses laser capture microdissection Mirror (Ji Ensi (キ ー エ Application ス) corporation, trade name：VK-9700 face profile) is measured with 50 times of multiplying power.Then, from To face profile surface roughness RMS and the average length RSm of roughness curve element are obtained based on JIS B0601 (2001) Value.
Anti-soil film, the low-reflection film to form a film in each example is relative to the very thin film of the thickness of transparent base, therefore surface Concaveconvex structure substantially directly make carbon copies transparent base surface shape.Therefore, (anti-soil film side is formed with for transparent base Face) surface shape, it is believed that it is 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.Mist degree is surveyed It is fixed, use haze meter (ス ガ testing machines Co. Ltd. system, model：HZ-V3 it) carries out.
(friction durability (wearability) is tested)
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 Durability test.
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 the planar metal pressure head of 10mm × 10mm in bottom surface, friction sample is made Friction head.
Then, using above-mentioned friction head, connect formula (Daiei science essence device corporation, model with plane abrasion testing machine 3：PA- 300A) carry out friction test.Specifically, it is installed in a manner that the bottom surface of above-mentioned pressure head is contacted with the antifouling film surface of sample first It on abrasion testing machine, and loads weight and causes to be 1000g to the load of friction head, in average speed 6400mm/ minute and singly It reciprocatingly slides under conditions of journey 40mm.Rubbing number is counted as by reciprocal 1 time 1 time, and in a manner that Rubbing number is 1000 times It is 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 corporation, model： DM-501), drip on anti-soil film and 1 μ L of pure water and measure 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 using its average value as the water contact angle after the durability test of the sample.
At this point, water contact angle is evaluated as qualification for 90 ° or more, 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, using using glass substrate (the Asahi Glass strain formula meeting that implements chemical intensification treatment Society's system, trade name：" Dragontrail " (registered trademark)) and defined frosted has been carried out to the first interarea of the glass substrate Glass substrate obtained from processing (is denoted as transparent base A) below.
Then, anti-soil film is formed with following step on the first interarea of transparent base A.
First, by fluorine-containing organic silicon compound (SHIN-ETSU HANTOTAI's Chemical Co., Ltd. system, trade name：KY-185 heating container) is imported It is interior to be used as evaporation material.Then, by heating container in using vacuum pump degassing 10 hours or more it is molten in solution to remove Agent, so as to which fluorine-containing organic silicon compound overlay film formation composition be made.
Next, the heating container equipped with above-mentioned fluorine-containing organic silicon compound film formation composition is heated to 270 DEG C. After reaching 270 DEG C, its state is kept for 10 minutes until temperature is stablized.
Then, to being arranged on the first interarea (face handled through frosted) of the indoor transparent base A of vacuum, 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 form a film.
During film forming, form a film while film thickness is measured by being arranged on the indoor crystal oscillator monitor of vacuum, Until the film thickness of fluorine-containing organic silicon compound film being 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 It is formed with the transparent base A of 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 that film surface is upward On, and at 150 DEG C be heat-treated within 60 minutes in an atmosphere.
For sample obtained in the above described manner, above-mentioned surface shape measuring is carried out, mist degree measures and friction durability examination It tests.Show the result in table 1.
[example 2]
As transparent base, using using the glass substrate (Asahi Glass Co., Ltd's system, the quotient that implement chemical intensification treatment The name of an article：" Dragontrail " (registered trademark)) and the first interarea of the glass substrate has been carried out frosted processing transparent base B in addition to this, anti-soil film is formed in a manner of same as Example 1 on the first interarea of transparent base B.Band obtained is prevented 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 the glass substrate (Asahi Glass Co., Ltd's system, the quotient that implement chemical intensification treatment The name of an article：" Dragontrail " (registered trademark)) and the first interarea of the glass substrate has been carried out frosted processing transparent base C in addition to this, anti-soil film is formed in a manner of same as Example 1 on the first interarea of transparent base C.Band obtained is prevented 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 mixed gas of oxygen of 10 volume % is mixed in 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, niobium oxide is included so as to form thickness 13nm on the first interarea of transparent base A (niobia) high refractive index layer.
Next, using silicon target in pressure while the mixed gas of oxygen of 40 volume % is mixed in importing argon gas 0.3Pa, frequency 20kHz, power density 3.8W/cm2, under conditions of 5 microsecond of reverse impulse width, in 5 microsecond of pulse width 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, niobium oxide target is used while the mixed gas of oxygen of 10 volume % is mixed in 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 It spends under conditions of 5 microseconds and carries out pulsed sputter, niobium oxide is included so as to form thickness 110nm on above-mentioned low-index layer (niobia) high refractive index layer.
Next, using silicon target in pressure while the mixed gas of oxygen of 40 volume % is mixed in importing argon gas 0.3Pa, frequency 20kHz, power density 3.8W/cm2, under conditions of 5 microsecond of reverse impulse width, in 5 microsecond of pulse width Under the conditions of carry out pulsed sputter and form the low-index layer for including silica (silica) of thickness 90nm.
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 transparent base obtained 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 the glass substrate (Asahi Glass Co., Ltd's system, the quotient that implement chemical intensification treatment The name of an article：" Dragontrail " (registered trademark)) and the first interarea of the glass substrate has been carried out frosted processing transparent base D in addition to this, anti-soil film is formed in a manner of same as Example 1 on the first interarea of transparent base D.Band obtained is prevented 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 the glass substrate (Asahi Glass Co., Ltd's system, the quotient that implement chemical intensification treatment The name of an article：" Dragontrail " (registered trademark)) and the first interarea of the glass substrate has been carried out frosted processing transparent base E in addition to this, anti-soil film is formed in a manner of same as Example 1 on the first interarea of transparent base E.Band obtained is prevented 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 to this, formed in a manner of same as Example 4 Low-reflection film and anti-soil film evaluate the transparent base obtained with anti-soil film in a manner of same as Example 1.By result It is shown in table 1.
[table 1]
Result according to table 1 it is found that about meet present invention provide that example 1~4, the water in the durability test that rubs Contact angle is 90 ° or more, and in contrast, about 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 becomes smaller represents anti-soil film stripping, abrasion.Therefore, About example 5~7, it is known that anti-soil film stripping, abrasion.
By these results it has been confirmed that about 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, about example 1~4, it can also be confirmed with 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 Be not limited to the above embodiment with embodiment etc..It can be in the range of the gist of the invention recorded in detail in the claims Carry out various modifications and changes.
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 numeral
11 transparent bases
12 anti-soil films
13 low-reflection films

Claims (8)

1. a kind of transparent base with anti-soil film, has：
With the first interarea and the transparent base of second interarea opposite with first interarea and
It is arranged on the anti-soil film comprising fluorine-containing organic silicon compound of the first interarea side of the transparent base and low anti- Penetrate film,
The surface roughness RMS of the anti-soil film be 0.05 μm or more and 0.25 μm hereinafter, and the coarse of the anti-soil film write music The average length RSm of line feature be 10 μm or more and 40 μm hereinafter, and
The low-reflection film, the anti-soil film are sequentially laminated on the surface of first interarea of the transparent base.
2. the transparent base with anti-soil film as described in claim 1, wherein, the mist degree of the transparent base with anti-soil film is More than 2% and less than 30%.
3. the transparent base with anti-soil film as claimed in claim 1 or 2, wherein, the transparent base is glass substrate.
4. the transparent base with anti-soil film as claimed in claim 3, wherein,
Concaveconvex shape is formed in first interarea of the transparent base,
The surface roughness RMS of first interarea of the transparent base is for 0.05 μm or more and 0.25 μm hereinafter, and described The average length RSm of the roughness curve element of first interarea of transparent base is 10 μm or more and less than 40 μm.
5. such as the transparent base according to any one of claims 1 to 4 with anti-soil film, wherein, the low-reflection film be containing The laminated body of layer and silicon oxide layer selected from one or more of niobium oxide, titanium oxide, zirconium oxide, silicon nitride and tantalum oxide.
6. such as the transparent base according to any one of claims 1 to 5 with anti-soil film, wherein, the low-reflection film is is laminated Laminated body obtained from multiple layers amounts in the laminated body and is laminated with 2 layers or more and less than 6 layers of layer.
7. such as the transparent base according to any one of claims 1 to 6 with anti-soil film, wherein, the surface of the anti-soil film is thick Rugosity RMS is 0.08 μm or more and less than 0.20 μm.
8. such as the transparent base according to any one of claims 1 to 7 with anti-soil film, wherein, the roughness of the anti-soil film The average length RSm of curve element is 15 μm or more and less than 35 μm.
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TW201434775A (en) 2014-09-16

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