CN104718465B - There is the manufacture method of the glass of antireflection and there is the glass of antireflection - Google Patents
There is the manufacture method of the glass of antireflection and there is the glass of antireflection Download PDFInfo
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- CN104718465B CN104718465B CN201380053816.4A CN201380053816A CN104718465B CN 104718465 B CN104718465 B CN 104718465B CN 201380053816 A CN201380053816 A CN 201380053816A CN 104718465 B CN104718465 B CN 104718465B
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- 239000011521 glass Substances 0.000 title claims abstract description 307
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 171
- 238000000034 method Methods 0.000 claims abstract description 109
- 239000007789 gas Substances 0.000 claims abstract description 80
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 59
- -1 fluoride compound Chemical class 0.000 claims abstract description 45
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 238000002835 absorbance Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- KRHYYFGTRYWZRS-UHFFFAOYSA-N HF Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 18
- 239000011737 fluorine Substances 0.000 claims description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 17
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- DTQVDTLACAAQTR-UHFFFAOYSA-N trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims 5
- 241000271566 Aves Species 0.000 claims 1
- 210000003746 Feathers Anatomy 0.000 claims 1
- 244000144992 flock Species 0.000 claims 1
- 239000002344 surface layer Substances 0.000 claims 1
- 238000007792 addition Methods 0.000 description 22
- 238000005530 etching Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 16
- 239000002689 soil Substances 0.000 description 16
- 230000000630 rising Effects 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 239000012159 carrier gas Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005755 formation reaction Methods 0.000 description 7
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 230000003373 anti-fouling Effects 0.000 description 4
- 238000004166 bioassay Methods 0.000 description 4
- 230000004301 light adaptation Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000005368 silicate glass Substances 0.000 description 4
- 239000005361 soda-lime glass Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 150000002221 fluorine Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003287 optical Effects 0.000 description 2
- 239000005304 optical glass Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static Effects 0.000 description 2
- LTOKKZDSYQQAHL-UHFFFAOYSA-N trimethoxy-[4-(oxiran-2-yl)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCC1CO1 LTOKKZDSYQQAHL-UHFFFAOYSA-N 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ETFE Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 210000003414 Extremities Anatomy 0.000 description 1
- PGFXOWRDDHCDTE-UHFFFAOYSA-N Hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N Hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 229950000845 Politef Drugs 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 210000003491 Skin Anatomy 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000005385 borate glass Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005039 chemical industry Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N p-acetaminophenol Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 238000005211 surface analysis Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Abstract
The present invention provides the manufacture method of the glass with antireflection, comprising: (a) is under normal pressure, air atmosphere, within the temperature range of 250 DEG C～650 DEG C, makes the step that the place's process gases comprising fluorine compounds contacts with the surface of glass substrate；And (b) forms the step of layer of organic fluoride compound on above-mentioned surface.
Description
Technical field
The present invention relates to the glass with antireflection.
Background technology
Such as building materials glass, display pannel glass, optical element, solar panel glass, glazing plate,
In the various glass such as optical glass and lens, it is sometimes desirable to high light transmission.In the case of Gai, use and there is antireflection
The glass substrate of property.
The glass substrate with such antireflection can be by such as infusion process at the low folding of the surface of glass substrate coating
Penetrate rate material, or constituted at the surface of glass substrate formation multilayer film by the dry process of vapour deposition method or sputtering method etc..
Prior art literature
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2009-529715 publication
Summary of the invention
Invent technical problem to be solved
As it has been described above, in the case of the glass of the high light transmission of manufacture requirements, can use by various methods at table
The glass substrate of antireflection film is defined on face.
, if using the glass being formed with such antireflection film, sometimes at the surface attachment water of glass
Point, oil, the dirt such as fingerprint and/or dust, the aesthetic feeling of infringement glass.
Even if accordingly, there exist for using for a long time, it is not easy on the surface of glass adhere to dirt, there is what is called
The demand of the glass of " soil resistance ".
Such as, in order to tackle this demand, it is considered at the layer of the surface configuration fluoride compound of glass.This is because usual fluorine
Compounds has soil resistance.
But, even if in the case of the surface configuration of glass substrate has the layer of fluoride compound, also can often confirm
In such glass substrate, the phenomenon that anti-fouling effect reduces in the short period of time or disappears.And, if it occur that such
Phenomenon, the effect that result is produced by arranging the layer of fluoride compound disappears, and causes starting attachment dirt the most on the glass substrate
Thing.
The present invention is the invention completed in view of the above problems, and it is an object of the invention to provide can long term maintenance soil resistance
The manufacture method of antireflection glass.Moreover, it is an object that play the antireflection glass of soil resistance for a long time.
Solve the technical scheme that technical problem is used
The present invention provides the manufacture method of the glass with antireflection, comprising: (a) is under normal pressure, air atmosphere,
Within the temperature range of 250 DEG C～650 DEG C, make the step that the place's process gases comprising fluorine compounds contacts with the surface of glass substrate；
And (b) forms the step of layer of organic fluoride compound on above-mentioned surface.
Here, in the manufacture method of a kind of form of the present invention, the layer of above-mentioned Organic fluoride compounds can be by coating
Process is formed on above-mentioned surface.
Additionally, in the manufacture method of a kind of form of the present invention, the layer of above-mentioned Organic fluoride compounds can bag fluorinated
Polymer and/or fluorine containing silane coupling agent.
Additionally, in the manufacture method of a kind of form of the present invention, as the raw material of above-mentioned place process gases, fluorination can be comprised
Hydrogen and/or trifluoroacetic acid.
Additionally, in the manufacture method of a kind of form of the present invention, above-mentioned place process gases can comprise hydrogen fluoride gas, and should
The concentration of hydrogen fluoride gas is in 0.1 volume %～the scope of 10 volume %.
Additionally, in the manufacture method of a kind of form of the present invention, above-mentioned place process gases can also comprise nitrogen and/or argon.
Additionally, in the manufacture method of a kind of form of the present invention, in the step of above-mentioned (a), above-mentioned glass substrate is permissible
Contact with above-mentioned place process gases when being handled upside down.
Additionally, in the manufacture method of a kind of form of the present invention, in the step of above-mentioned (a), at above-mentioned glass substrate
Top configuration ejector, above-mentioned place process gases can be sprayed towards above-mentioned glass substrate from above-mentioned ejector.
In the case of Gai, above-mentioned glass substrate can be between 1 second～120 seconds by the time of above-mentioned ejector.
Additionally, in the manufacture method of a kind of form of the present invention, the layer of above-mentioned Organic fluoride compounds and the contact angle of water
Can be more than 90 °.
Additionally, in the manufacture method of a kind of form of the present invention, can have between above-mentioned (a) and the step of (b)
Above-mentioned surface forms the step of close binder.
The present invention also provides for the glass with antireflection, comprising: have the glass substrate on surface, with on above-mentioned surface
The layer of the Organic fluoride compounds of upper formation；The above-mentioned surface of above-mentioned glass substrate has nano level concavo-convex；Above-mentioned glass base
The above-mentioned surface of plate has the part that compared with main body silica concentration declines, composition beyond silicon is more.
Here, in the glass of a kind of form of the present invention, at above-mentioned glass substrate and the layer of above-mentioned Organic fluoride compounds
Between can also have close binder.
Additionally, in the glass of a kind of form of the present invention, the layer of above-mentioned Organic fluoride compounds can comprise fluoropolymer
Thing and/or fluorine containing silane coupling agent.
Additionally, in the glass of a kind of form of the present invention, the thickness of slab of above-mentioned glass substrate is below 3mm, and this glass base
The absorbance (meansigma methods of the absorbance in the range of wavelength 400nm～700nm) of plate can be more than 88%.
The effect of invention
The present invention can provide the manufacture method of the antireflection glass of long term maintenance soil resistance.Additionally, the present invention can
The long-term antireflection glass playing soil resistance is provided.
Accompanying drawing explanation
Fig. 1 is the figure of the flow process of the manufacture method of the antireflection glass illustrating one embodiment of the invention briefly.
Fig. 2 is under the state being shown in moving glass substrate, for implementing the processing means of the etch processes of glass substrate
The figure of a configuration example.
Fig. 3 is the sectional view of the antireflection glass illustrating one embodiment of the invention briefly.
Fig. 4 is the cross section SEM photograph of the glass substrate after etch processes.
Detailed description of the invention
Hereinafter, referring to the drawings a kind of form of the present invention is described in detail.
The present invention provides the manufacture method of the glass with antireflection, comprising: (a) is under normal pressure, air atmosphere,
Within the temperature range of 250 DEG C～650 DEG C, make the step that the place's process gases comprising fluorine compounds contacts with the surface of glass substrate；
And (b) forms the step of layer of organic fluoride compound on above-mentioned surface.
As it has been described above, in the case of the glass of the high light transmission of manufacture requirements, can use by various methods at table
The glass substrate of antireflection film is defined on face.
On the other hand, in being formed with the use of glass of such antireflection film, sometimes on the surface of glass
The dirts such as adhesive water, oil, fingerprint and/or dust, the aesthetic feeling of infringement glass.Even if making for a long time it is therefore desirable to a kind of
With, it is not easy on the surface of glass adhere to dirt, there is the glass of what is called " soil resistance ".
In order to tackle this demand, such as, consider the layer of surface configuration fluoride compound at glass.This is because usual fluorine
Compounds has soil resistance.
But, according to the research of present inventor, though the layer of the surface configuration fluoride compound at glass substrate, also
Usually confirm that anti-fouling effect reduces or disappears within a short period of time.Think that its reason is, in the use of glass substrate, fluorine class
The layer of compound is slowly lost or peels off, and the amount of the fluoride compound existed on the surface of glass substrate reduces.Particularly make glass
In the case of glass substrate shows antireflection, form antireflection film on the surface of glass substrate.Generally, the film of this antireflection film
It is thick relatively thin, so the surface of glass substrate must be relatively flat.This is because, if it is not, be then difficult at glass substrate
Required whole surface accuracy good and be formed uniformly antireflection film.
But, in the case of the smooth surface of glass substrate forms the layer of fluoride compound, the layer of fluoride compound
It is easier to loss occurs and/or peels off.Additionally, due to this reason, cause above-mentioned phenomenon, i.e. anti-fouling effect within a short period of time
The problem reduced or disappear is more significantly.
To this, first the manufacture method of the glass of present embodiment has the feature that, utilizes the place comprising fluorine compounds
Process gases etch processes glass substrate, afterwards, the surface after this etch processes forms the layer of organic fluoride compound.
In present embodiment, because form the layer of organic fluoride compound on the surface of glass substrate, so glass substrate
Take this to show soil resistance.
Additionally, as the replacement of conventional antireflection film, by use process gases etch processes glass substrate, at glass base
The surface of plate is formed fine concavo-convex, takes this to make glass substrate show antireflection.
In the case of Gai, the layer of Organic fluoride compounds be arranged on glass baseplate surface, and the surface of this glass substrate is not flat
Smooth surface, but by the etch processes of preceding processes, form the finest nano level concavo-convex surface.Therefore, originally
In embodiment, the layer of Organic fluoride compounds is not susceptible to the loss in using and/or stripping, it is possible to long term maintenance is antifouling
Property.
Due to above effect, the manufacture method of present embodiment can provide the long-time antireflection maintaining soil resistance
Glass.
It addition, in the application, " etch processes " refers to unrelated with actual etch quantity, and at use, process gases makes glass substrate
Surface exhibits go out the process of antireflection.Therefore, even the process that actually etch quantity is few (such as formed 0.1nm～
The process of the concavo-convex level of 200nm level), as long as making the surface exhibits of glass substrate go out antireflection, then such process
It is also contained in " etch processes ".In this sense, what " etch processes " can also be expressed as process gases at employing " gives anti-
Reflexive process ".
Additionally, " nano level concavo-convex " refers to the concavo-convex of below 1 μm, preferably below 500nm, more preferably below 300nm.But
It is, in the range of the effect not damaging the application, it is not excluded that the concavo-convex existence of below 1nm.
(about the manufacture method of one embodiment of the invention)
Then, referring to the drawings, the manufacture method for the antireflection glass of one embodiment of the invention is carried out specifically
Bright.
Fig. 1 illustrates the flow process of the manufacture method of the glass of one embodiment of the invention briefly.
As it is shown in figure 1, the manufacture method of the glass of one embodiment of the invention includes: (a) under normal pressure, air atmosphere,
Within the temperature range of 250 DEG C～650 DEG C, make the step that the place's process gases comprising fluorine compounds contacts with the surface of glass substrate
(step S110)；And (b) forms the step (step S120) of layer of organic fluoride compound on above-mentioned surface.
Below each step is illustrated.
(step S110)
First, glass substrate is prepared.
The kind of glass substrate is not particularly limited.As glass substrate, can use such as by soda-lime glass, sodium calcium silicon
Silicate glass, alumina silicate glass, borate glass, lithium alumina silicate glass, quartz glass, pyrex, alkali-free glass,
And the transparent glass substrate that other various glass are constituted.
The particularly preferred soda lime glass of glass substrate or alumina silicate glass are such containing alkali metal, alkaline earth
Metallic element and/or the glass of aluminum.
In the case of glass substrate contains alkali metal, alkali earth metal and/or aluminum, after etch processes,
The easy residual fluorinated compound in surface of glass substrate.
Such residual fluorinated compound is conducive to improving the light transmission of glass substrate.That is, the refraction of residual fluorinated compound
Rate (n1) it is generally of the refractive index (n of glass substrate2) and the refractive index (n of air0Refractive index between).Therefore, by successively
Configuration glass substrate, fluorine compounds and air, overall reflectance reduction, the light transmission of result glass substrate improves.
Glass substrate preferably has high absorbance, the transmission of such as more than 80% in the wavelength region of 350nm～800nm
Rate.Additionally, glass substrate preferably has enough insulating properties, chemically and physically durability is high.
The manufacture method of glass substrate is not particularly limited.Glass substrate can be manufactured by such as float glass process.
The thickness of glass substrate is not particularly limited, can be in the range of such as 0.1mm～12mm.
It addition, glass substrate needs not be plane, glass substrate can also be curved, different form, the most permissible
Forming rolls surface detail when being to be formed with forming of glass on surface, the glass that is referred to as " matrixes for embossing (Japanese: template) ".
Then, glass substrate is exposed in the place's process gases comprising fluorine compounds, implements the etch processes of glass substrate.
This etch processes can be implemented under the air atmosphere of normal pressure.
This operation be the fine concavo-convex of the rank in order to form such as 0.1nm～200nm on the surface of glass substrate and
Implement.By the concavo-convex existence that these are fine, give glass substrate antireflection.
Etch processes is implemented in the range of 250 DEG C～650 DEG C.Treatment temperature is preferably 275 DEG C～the scope of 600 DEG C,
More preferably 300 DEG C～the scope of 600 DEG C.
About the kind of the fluorine compounds used in etch processes, as long as comprise fluohydric acid gas when the etching of glass surface
Gas, be just not particularly limited.As the raw material of the place's process gases comprising fluorine compounds, can be such as fluohydric acid gas and/or
Trifluoroacetic acid.Fluohydric acid gas, trifluoroacetic acid are unexplosive material, so it is preferred for considering from a security point.Trifluoro
Acetic acid, by the temperature thermal decomposition of glass surface, produces fluohydric acid gas.
Place's process gases, in addition to containing fluorine compounds, can contain carrier gas.As carrier gas, there is no particular limitation as to it, can make
With such as nitrogen and/or argon etc..Even if even water.
As long as the concentration of the fluorine compounds in place's process gases can the surface of suitably etch processes glass substrate, just there is no spy
Do not limit.The concentration of the fluorine compounds in place's process gases is such as 0.1 volume %～the scope of 10 volume %, preferably 0.5 body
Long-pending %～the scope of 8 volume %, more preferably 1 volume %～the scope of 5 volume %.
By the process of process gases at employing, the surface of etching glass substrate.
Here, use containing the oxidation in the etch processes of place's process gases of fluorine compounds, in preferential removing glass substrate
Silicon.Therefore, can confirm that the concentration of the silicon oxide on the surface after the etch processes of glass substrate is lower than main body, silicon oxide on the contrary
The tendency that the concentration of composition in addition rises.
Such feature easily can be known by the XPS analysis etc. on the surface of such as glass substrate.
It addition, the etch processes of glass substrate can be implemented when moving glass substrate.In the case of Gai, it is possible to realize
Process more rapidly.
Under the state that Fig. 2 is shown in moving glass substrate 180, for implementing the processing means of the etch processes of glass substrate
A configuration example.It addition, in following record, as an example, hydrogen fluoride gas will be used as the process comprising fluorine compounds
Illustrate in case of the raw material of gas.
As in figure 2 it is shown, this processing means 100 possesses ejector 110 and handling unit 150.
Handling unit 150 can be by mounting glass substrate 180 to its upper along the horizontal direction (X shown in arrow F201
Direction) carry.
Ejector 110 is arranged in handling unit 150 and the top of glass substrate 180.
Ejector 110 has multiple slits 115,120 and 125 of the stream of place's process gases.That is, ejector 110 possesses:
At the 1st slit 115 that middle body is arranged along vertical (Z-direction)；Along vertical in the way of surrounding the 1st slit
The 2nd slit 120 that (Z-direction) is arranged；With arranged along vertical (Z-direction) in the way of surrounding the 2nd slit 120
3 slits 125.
One end (top) of 1st slit 115 is connected with hydrogen fluoride gas source (not shown), the other end of the 1st slit 115
(bottom) is orientated towards the direction of glass substrate 180.Similarly, one end (top) of the 2nd slit 120 is with carrier gas source (not shown) even
Connecing, the other end (bottom) of the 2nd slit 120 is orientated towards the direction of glass substrate 180.One end (top) of 3rd slit 125 and row
Gas system (not shown) connects, and the other end (bottom) of the 3rd slit 125 is orientated towards the direction of glass substrate 180.
Use processing means 100, in the case of implementing the etch processes of glass substrate 180, first from hydrogen fluoride gas source
(not shown) passes through the 1st slit 115, and the direction along arrow F205 supplies hydrogen fluoride gas.Additionally, lead to from carrier gas source (not shown)
Crossing the 2nd slit 120, the direction along arrow F210 supplies the carrier gas of nitrogen etc..These gases along arrow F215 to horizontal direction (X side
To) mobile after, utilize gas extraction system, be removed to the outside of processing means 100 by the 3rd slit 125.
It addition, in the 1st slit 115, hydrogen fluoride gas and carrier gas can be supplied simultaneously to.
Glass substrate 180 utilizes handling unit 150, and the direction along arrow F201 is handled upside down.
Glass substrate 180 is when by the downside of ejector 110, with the place from the 1st slit the 115 and the 2nd slit 120 supply
Process gases (hydrogen fluoride gas+carrier gas) contacts.Taking this, the surface of glass substrate 180 is etched process.
It addition, the place's process gases supplying the surface to glass substrate 180 moves along arrow F215 and is used at etching
After reason, move along arrow F220, by the 3rd slit 125 being connected with gas extraction system, be removed to the outside of processing means 100.
By using processing means 100, can moving glass substrate, while the surface of process gases at enforcement utilization
Etch processes.In the case of Gai, compared with the method using reaction vessel enforcement etch processes, it is possible to increase treatment effeciency.Additionally,
In the case of using processing means 100, it is also possible to large-scale glass substrate application etch processes.
Here, the feed speed of process gases at glass substrate 180 supply is not particularly limited.The confession of place's process gases
Can be the scope of such as 5SLM～1000SLM (volume (liter) of the gas of internal standard state per minute) to speed.
Additionally, the transporting velocity of glass substrate 180 is such as 1m/ minute～20m/ minute.
Additionally, glass substrate 180 is 1 second～the scope of 120 seconds by the time of ejector 110, preferably 5 seconds～60 seconds
Scope, more preferably 5 seconds～the scope of 30 seconds.By glass substrate 180 was set to less than 120 seconds by the time of ejector 110,
Quick etch processes can be implemented.
Here, refer to " by the time of ejector 110 " that certain regulation region of glass substrate 180 is by distance S of Fig. 2
Time.It addition, distance S is by the carrying direction of glass substrate 180, the slit from the side, most upstream of ejector 110 be (Fig. 2's
Slit 125 in example) upstream extremity to the distance between the downstream of the slit (slit 125 in the example of Fig. 2) of most downstream side
Determine.
Thus, by using processing means 100, it is possible to the glass substrate of carrying state is implemented etch processes.
It addition, the processing means 100 shown in Fig. 2 is only an example, it is possible to use other device, implements utilization and comprise fluorine
Change the etch processes of the glass substrate of place's process gases of hydrogen.Such as, in the processing means 100 of Fig. 2, glass substrate 180 phase
Relative movement is carried out for static ejector 110.But it is also possible in contrast, make ejector relative to static glass
Substrate moves in the horizontal direction.Or, it is possible to make glass substrate and ejector both sides move the most in the opposite direction.
Additionally, in the processing means 100 of Fig. 2, ejector 110 has three slits 115,120,125 altogether.But, to narrow
The quantity of seam is not particularly limited.Such as, the quantity of slit can be two.In the case of Gai, can be that a slit is used for
Process gases (carrier gas and the mixed gas of hydrogen fluoride gas) at supply, another slit is used for aerofluxus.
Further, in the processing means 100 of Fig. 2, the 2nd slit 120 of ejector 110 is joined in the way of surrounding the 1st slit 115
Putting, the 3rd slit 125 is arranged in the way of surrounding the 1st slit the 115 and the 2nd slit 120.But, instead, can be narrow by the 1st
Seam, the 2nd slit and the 3rd slit (X-direction) in the horizontal direction are arranged in string.In the case of Gai, place's process gases be at glass substrate
Surface is moved along a direction, is then discharged by the 3rd slit.
By above operation, it is possible to give glass substrate antireflection.
(step S120)
Then, the layer of the etching surface configuration Organic fluoride compounds of the glass substrate after being processed by aforesaid operation.
Method to set up for the layer of Organic fluoride compounds is not particularly limited.Such as, the layer of Organic fluoride compounds
The etching surface of glass substrate can be arranged on by cladding process.As cladding process, such as rubbing method or infusion process etc. can be used.
Hereinafter, as an example, to by rubbing method in the side of the layer of the surface configuration Organic fluoride compounds of glass substrate
Method illustrates.
In the case of Gai, as described below, first prepare the solution comprising organic fluoride compound, use this solution to be formed organic
The layer of fluoride compound.
(preparation of solution)
First, the solution being coated with on the surface of glass substrate is prepared.
Solution comprises organic fluoride compound and solvent.
Organic fluoride compounds can comprise such as fluorine-based polymer and/or fluorine containing silane coupling agent.
As fluorine-based polymer, such as politef, poly-trifluoro-ethylene, polyvinyl fluoride, Kynoar can be enumerated, gather
Perfluoroalkyl vinyl ether, poly(perfluoropropene), politef-perfluoropropene copolymer, tetrafluoroethylene-ethylene copolymer and
Polyvinyl fluoride-ethylene copolymer etc..
Additionally, in these materials, the thing having imported the hydroxyl as functional group, amino, epoxy radicals, carboxyl etc. can be used
Matter.Additionally, fluoropolyether class or fluorine-containing poly-(methyl) esters of acrylic acid etc. can be used.
As the representational compound of polyethers, there are perfluorinated ethylene oxide, perfluoro propene oxid, perfluor methylene oxygen-complete
Fluorine propylene oxide copolymer, perfluor methylene oxygen-perfluor ethylene oxide copolymer, perfluorinated ethylene oxide-perfluoro propene oxid copolymerization
Thing etc..
Additionally, polyethers can be have in the end or strand of above-mentioned fluorochemical polyether carboxyl, hydroxyalkyl, ester group or
The compound of NCO etc..
Additionally, as the representative compound of (methyl) esters of acrylic acid, poly-trifluoroethyl (methyl) acrylic acid can be enumerated
Ester, polytetrafluoro propyl group (methyl) acrylate, poly-octafluoro amyl group (methyl) acrylate, poly-17 fluorine decyl (methyl) acrylic acid
Ester, the copolymer of fluorine-containing (methyl) acrylate or fluorine-containing (methyl) acrylate and other (methyl) acrylate, such as
The copolymer etc. of (methyl) acrylic acid methyl ester., (methyl) 2-(Acryloyloxy)ethanol, (methyl) glycidyl acrylate etc..
Also they can be used in mixed way.
Additionally, as fluorine containing silane coupling agent, such as have CF3(CF2)7CH2CH2Si(OCH3)3、CF3(CF2)7CH2CH2SiCl3、CF3(CF2)7CH2CH2Si(CH3)(OCH3)2、CF3(CF2)7CH2CH2Si(CH3)C12、CF3(CF2)5CH2CH2SiCl3、CF3(CF2)5CH2CH2Si(OCH3)3、CF3CH2CH2SiCl3、CF3CH2CH2Si(OCH3)3、C8F17SO2N
(C3H7)CH2CH2CH2Si(OCH3)3、C7F15CONHCH2CH2CH2Si(OCH3)3、C8F17CO2CH2CH2CH2Si(OCH3)3、C8F17-
O-CF(CF3)CF2-O-C3H6SiCl3、C3F7-O-(CF(CF3)CF2-O)2-CF(CF3)CONH-(CH2)3Si(OCH3)3Deng.They
Can be used alone, it is also possible to be used in mixed way.In addition, it is possible to make again after making partial hydrolysis condensate with acid or alkali etc. in advance
With.
Additionally, as silicon nitrogen silane compound, hexamethyldisiloxane, CF can be enumerated3(CF2)7CH2CH2Si(NH)3/2Deng.Also
Use after they can be mixed.In addition, it is possible to re-use after making partial hydrolysis condensate with acid or alkali etc. in advance.
On the other hand, as solvent, there are such as fluorine kind solvent, aliphatic category solvent, ketones solvent and esters solvent etc..
Additionally, solution also can contain additive.As additive, such as adhesion promotor, firming agent and solidification can be enumerated
Catalyst etc..
(formation of the layer of Organic fluoride compounds)
Then, aforesaid solution is coated on the surface of glass substrate.
Coating process is not particularly limited.Solution can use such as spin-coating method, spraying process, rolling method and flow coat method
Etc. the surface being coated on glass substrate.
Then, by being dried by solution, form the layer of organic fluoride compound on the surface of glass substrate.
In the case of necessity, when solidifying the layer of organic fluoride compound, glass substrate can be carried out heat treatment.Heat treatment
Temperature the highest can be below 200 DEG C.
Take this, the Organic fluoride of thickness for example, 1nm～100nm can be formed on the surface being etched process of glass substrate
The layer of compounds.
It addition, the layer of Organic fluoride compounds can be formed directly on the surface being etched process of glass substrate, but make
For other forms, it is possible to make close binder be present in the downside of layer of Organic fluoride compounds.
By there is close binder, can further improve the adaptation between the layer of glass substrate and Organic fluoride compounds.
As long as close binder can improve above-mentioned adaptation, its material is just not particularly limited.Close binder can be by such as
γ-glycidylpropyl trimethoxy silane, 3-glycidylpropyl trimethoxy silane, 2-(3,4-epoxycyclohexyethylSiOi
Base) ethyl trimethoxy silane, tetramethoxy-silicane, tetraethoxysilane and/or gamma-amino propyl trimethoxy silicane etc.
The silazane compounds such as silane coupler or Perhydropolysilazane is constituted.
By above operation, it is possible to manufacture the antireflection glass with soil resistance.
It addition, in the application, the soil resistance of glass (or layer of Organic fluoride compounds) can be according to the water of subject surface
Contact angle judges.I.e., it is possible to say the surface that the contact angle of water is the biggest, soil resistance is the best.
(about the glass of one embodiment of the invention)
Then, referring to the drawings, the glass of one embodiment of the invention is illustrated.
Fig. 3 illustrates the cross section of the glass of one embodiment of the invention briefly.
As it is shown on figure 3, the glass 300 of one embodiment of the invention has glass substrate 310, close binder 320 and Organic fluoride
The layer 330 of compounds.It addition, Fig. 3 is the simple figure represented, the most corresponding with actual size, and the component of a part overstates
Open ground to represent, this is needed to pay attention to.
Glass substrate 310 has the 1st surface 312, and the 1st surface has fine concavo-convex.Due to the 1st surface 312
Shape effects, gives glass 300 antireflection.
Additionally, the concentration of the silicon oxide on the 1st surface of glass substrate 310 is lower than main body, on the contrary beyond silicon oxide
The concentration of composition is higher than main body.
Close binder 320 is arranged on the 1st surface 312 of glass substrate 310.Close binder 320 is to improve Organic fluoride
The adaptation of glass substrate 310 is arranged by the layer 330 of compounds.
Close binder 320 is not limited to this, it is possible to be made up of such as tetraethoxysilane etc..But, close binder 320 also may be used
To omit.
It addition, the surface of close binder 320 does not have smooth shape, and to become the 1st surface along glass substrate 310
The mode of fine concavo-convex shape formed.By close binder 320 is made this shape, glass substrate 310 can be maintained
The shape effects on the 1st surface 312, i.e. the antireflection of glass 300 can be maintained.
The layer 330 of Organic fluoride compounds is arranged on close binder 320.Or, in the situation that there is not close binder 320
Under, the layer 330 of Organic fluoride compounds may be provided on the 1st surface 312 of glass substrate 310.
The layer 330 of Organic fluoride compounds has the thickness of 1nm～100nm.
The surface of the layer 330 of Organic fluoride compounds does not have smooth shape, and to become along glass substrate 310
The mode of the fine concavo-convex shape on the 1st surface is formed.By the layer 330 of Organic fluoride compounds is made this shape,
The shape effects on the 1st surface 312 of glass substrate 310 can be maintained, i.e. the antireflection of glass 300 can be maintained.
Additionally, make glass 300 show soil resistance by the layer 330 of Organic fluoride compounds.
The absorbance of the glass 300 of one embodiment of the invention is more than 91%.It addition, in the application, absorbance represents
The meansigma methods of the absorbance in the range of wavelength 400nm～700nm.
Additionally, the contact angle of the water of the layer 330 of Organic fluoride compounds is more than 90 °.The layer 330 of Organic fluoride compounds
The contact angle of water preferably more than 92 °, more preferably more than 95 °.
Here, the layer 330 of Organic fluoride compounds is arranged on the 1st surface 312 of glass substrate 310.On the 1st surface
On 312, the substantial amounts of fine concavo-convex shape staggered with dimensionally complexity is constituted.Additionally, layer 330 shape of Organic fluoride compounds
Become on the surface of minute concave-convex structure of this three-dimensional.Therefore, in glass 300, Organic fluoride compounds can be suppressed significantly
Layer 330 consumes because of abrasion or stripping or disappears.Additionally, take this can maintain " soil resistance " for a long time.
Due to above feature, the glass 300 of one embodiment of the invention is obtained in that antireflection, and can long time
Between maintain " soil resistance ".
Embodiment
Then, embodiments of the invention are illustrated.
(embodiment 1)
Manufacture antireflection glass by following method, its characteristic is evaluated.
(etch processes)
First, the glass substrate (soda-lime glass) to thickness 3mm implements to use the etch processes of HF gas.Etch processes
In, use the processing means 100 shown in aforesaid Fig. 2.
In processing means 100, in the 1st slit 115, the flow velocity with the 34cm/ second supplies hydrogen fluoride gas and the mixing of nitrogen
Gas.The quantity delivered of hydrogen fluoride gas is 1.0SLM (volume (liter) of the gas of internal standard state per minute), the supply of nitrogen
Amount is 31.0SLM (volume (liter) of the gas of internal standard state per minute).Additionally, mixed gas is with the shape being heated to 150 DEG C
State supplies.
Additionally, the flow velocity with the 34cm/ second supplies nitrogen in the 2nd slit 120.The temperature of nitrogen is 150 DEG C, the confession of nitrogen
Give amount for 10SLM.
Hydrogen fluoride gas is 2.4 volume % relative to the concentration of aggregate supply gas.
The capacity discharged from the 3rd slit 125 is supplied with 2 times of quantity delivered of gas.
The transporting velocity of glass substrate is 2m/ minute, and glass substrate is carried when being heated to 560 DEG C.It addition,
The temperature of glass substrate be will supply place's process gases before, use the value that records of radiation thermometer.
Etch processes time (in Fig. 2, the glass substrate time by distance S) is about 10 seconds.
Fig. 4 is to use scanning electron microscope (SEM) (high-tech Co., Ltd. of Hitachi (Hitachi Ha イ テ Network ノ ロ ジ
ズ society) system, SU70) take pictures obtained by, the sectional view of glass substrate after etch processes, knowable to this figure, in etch processes
After the process surface of glass substrate be formed substantial amounts of nano level concavo-convex.Hereinafter, the glass substrate in this stage is claimed especially
For " glass substrate after the etching of embodiment 1 ".
Use spectrophotometer (UV-3100: Shimadzu Corporation's system), measure glass after the etching of embodiment 1
The absorbance of substrate.The mensuration of absorbance is to make the etch processes face incidence of light glass substrate after the etching of embodiment 1, as
Integrating sphere absorbance is measured.Meansigma methods in the wave-length coverage of 400nm～700nm is denoted as absorbance Te。
Then, same for not implementing the glass substrate enforcement of etch processes mensuration.The absorbance obtained is denoted as
T0。
According to two absorbancies TeAnd T0Difference (Te-T0), calculate the absorbance rising value Δ T caused by etch processese(%).
The absorbance rising value Δ T of glass substrate after the etching of embodiment 1eIt is 2.0% (Te=92.3%, T0=
90.3%).
(formation of the layer of Organic fluoride compounds)
Then, after the etching of the embodiment 1 obtained by aforesaid method, following side on the surface of glass substrate, is passed through
Method forms the layer of organic fluoride compound.
The etch processes face spin coating CT-K solution (Asahi Glass Co., Ltd's system) of glass substrate after the etching of embodiment 1.
It addition, CT-K solution is by molten for the polymer of fluorine-containing methacrylic resin (perfluoro hexyl ethylmethyl acrylate C6FMA)
Solution is in solution (solid constituent 2%) obtained by fluorine kind solvent AC6000.The condition of spin coating be rotating speed 1000rpm, 10 seconds.
Then, glass substrate after the etching of embodiment 1 is put in stove, implement the dried of 30 minutes at 110 DEG C.
Take this, after the etching of embodiment 1, on glass substrate, form the layer of organic fluoride compound.Below, will obtain
Glass substrate is referred to as " glass of embodiment 1 ".
(evaluation)
Use the glass of embodiment 1, by aforesaid method, carry out the mensuration of absorbance.Measurement result is: embodiment 1
Absorbance T of glass1It is 92.6%.Additionally, absorbance rising value Δ the T (=T of the glass of embodiment 11-T0) it is 2.3%,
Identical with before the layer of the organic fluoride compound of formation, obtain high absorbance.It follows that the glass of embodiment 1 has
Significantly higher antireflection.
Then, use the glass of embodiment 1, carry out the mensuration of the contact angle of water.The contact angle of water is the glass in embodiment 1
Drip distilled water 1 μ L on the layer of the Organic fluoride compounds of glass, be measured after 30 seconds.In mensuration use contact angle meter (CA-X:
Consonance interface science Co., Ltd. (with interface science society) system).
The result measured is: the contact angle of water is 117 °.It addition, after the etching of embodiment 1 in glass substrate, carry out same
The mensuration of sample, the contact angle of result water is 10 °.Therefore confirming the layer by forming organic fluoride compound, contact angle is obvious
Rise, it is thus achieved that water repellency.
Then, the glass of embodiment 1 is implemented wipe test.
This wipe test is by after the surface wipes 20 times of glass with moistening cloth, evaluates the change of the characteristic of glass.Wiping
Test is by the moistening cloth of the face side water retting of the layer defining Organic fluoride compounds to the glass of embodiment 1
(BEMCOT AZ-8: Asahi Chemical Ind (Asahi Chemical Industry せ ん い society) system) wiping is implemented for 20 times.
After wipe test, measure absorbance T of the glass of embodiment 1a.Additionally, from this absorbance Ta, calculate in absorbance
Appreciation Δ Ta(=Ta-T0).Absorbance rising value Δ TaIt is 2.0%.It may thus be appreciated that the glass of embodiment 1 after wipe test also
Show good low reflexive.
Additionally, after wipe test, measure contact angle, result in the layer side of the Organic fluoride compounds of the glass of embodiment 1
The contact angle of water is 110 °.It may thus be appreciated that the glass of embodiment 1 also shows good water repellency after wipe test.
In the hurdle of the embodiment 1 of table 1 below, by manufacturing condition and the glass of embodiment 1 of the glass of embodiment 1
Evaluating characteristics result collect and illustrate.
[table 1]
(embodiment 2)
By method similarly to Example 1, manufacture the glass of embodiment 2, evaluate its characteristic.But, this embodiment 2
In, in the operation of (formation of the layer of Organic fluoride compounds), (hereinafter referred to as " real for the glass substrate after etch processes
Glass substrate after executing the etching of example 2 ") the spincoating conditions of CT-K solution be set to rotating speed 2000rpm and 20 seconds time.Other
Manufacturing condition is identical with the situation of embodiment 1.
Take this to obtain " glass of embodiment 2 ".
It addition, the absorbance of glass substrate rises after the etching of the embodiment 2 calculated according to method same as in Example 1
Value Δ Te(%) it is 2.0% (Te=92.3%, T0=90.3%).
Then, use the glass of embodiment 2, carried out the mensuration of absorbance by aforesaid method.The result measured is: real
Execute absorbance T of the glass of example 22It is 92.5%.Additionally, absorbance rising value Δ the T (=T of the glass of embodiment 22-T0) it is
2.2%, with formed organic fluoride compound layer before identical, obtained high absorbance.It follows that the glass of embodiment 2
Glass has significantly higher antireflection.
Then, use the glass of embodiment 2, carried out the mensuration of the contact angle of water by aforesaid method.The result measured
For: the contact angle of water is 118 °.It addition, after the etching of embodiment 2 in glass substrate, carry out same mensuration, result water
Contact angle is 10 °.Therefore confirming the layer by forming organic fluoride compound, contact angle substantially rises, it is thus achieved that water repellency.
Then, the glass to embodiment 2 implements aforesaid wipe test.Absorbance rising value Δ T after wipe testa
It is 2.0%.It may thus be appreciated that the glass of embodiment 2 is after wipe test, also show good low reflexive.Additionally, in wiping
The layer side of the Organic fluoride compounds of the glass of the embodiment 2 after test measures contact angle, and the contact angle of result water is 105 °.Cause
Knowable to this, the glass of embodiment 2 is after wipe test, also shows good water repellency.
In the hurdle of the embodiment 2 of aforesaid table 1, by manufacturing condition and the glass of embodiment 2 of the glass of embodiment 2
Evaluating characteristics result collect and illustrate.
(embodiment 3)
By method similarly to Example 1, manufacture the glass of embodiment 3, evaluate its characteristic.But, in this embodiment 3
In, by following method glass substrate (hereinafter referred to as " glass substrate after the etching of embodiment 3 ") shape after etch processes
Become the layer of Organic fluoride compounds.
Spin coating solution on the etch processes face of glass substrate after the etching of embodiment 3.As solution, use ォ Block Star
One Le DSX solution (Daikin Co., Ltd's system: the fluorine containing silane coupling agent comprising perfluor base and hydrolyzable silyl group) uses fluorine class
Solvent dilution is to solution obtained by 1%.The condition of spin coating is rotating speed 2000rpm, and the time is 20 seconds.
Then, glass substrate after the etching of embodiment 3 is put in stove, implement the dried of 30 minutes at 120 DEG C.
Take this to obtain " glass of embodiment 3 ".
It addition, the absorbance of glass substrate rises after the etching of the embodiment 3 calculated according to method same as in Example 1
Value Δ Te(%) it is 2.0% (Te=92.3%, T0=90.3%).
Then, use the glass of embodiment 3, carried out the mensuration of absorbance by aforesaid method.The result measured is: real
Execute absorbance T of the glass of example 33It is 92.5%.Additionally, absorbance rising value Δ the T (=T of the glass of embodiment 33-T0) it is
2.2%, with formed organic fluoride compound layer before identical, obtained high absorbance.It follows that the glass of embodiment 3
Glass has significantly higher antireflection.
Then, use the glass of embodiment 3, carried out the mensuration of the contact angle of water by aforesaid method.The result measured
For: the contact angle of water is 120 °.It addition, after the etching of embodiment 3 in glass substrate, carry out same mensuration, result water
Contact angle is 10 °.Therefore confirming the layer by forming organic fluoride compound, contact angle substantially rises, it is thus achieved that water repellency.
Then, the glass to embodiment 3 implements aforesaid wipe test.Absorbance rising value Δ T after wipe testa
It is 2.0%.It may thus be appreciated that the glass of embodiment 3 is after wipe test, also show good low reflexive.Additionally, in wiping
The layer side of the Organic fluoride compounds of the glass of the embodiment 3 after test measures contact angle, and the contact angle of result water is 115 °.Cause
This glass understanding embodiment 3 also shows good water repellency after wipe test.
(comparative example 1)
By method similarly to Example 1, manufacture the glass of comparative example 1, evaluate its characteristic.But, at this comparative example 1
In, glass substrate is not implemented etch processes.That is, glass substrate is only implemented the aforesaid (layer of Organic fluoride compounds
Formation) operation.Other manufacturing condition is identical with the situation of embodiment 1.
Take this, available " glass of comparative example 1 ".
Then, use the glass of comparative example 1, carried out the mensuration of absorbance by aforesaid method.The result measured is: ratio
Relatively absorbance T of the glass of example 14It is 90.8%.Additionally, absorbance rising value Δ the T (=T of the glass of comparative example 14-T0) it is
0.5% (T0=90.3%).
Then, use the glass of comparative example 1, carried out the mensuration of the contact angle of water by aforesaid method.The result measured
For: the contact angle of water is 105 °.It addition, in forming the glass substrate before the layer of organic fluoride compound, carried out same
Mensuration, result be the contact angle of water be 6 °.
Then, the glass to comparative example 1 implements aforesaid wipe test.Absorbance rising value Δ T after wipe testa
It is 0.1%.Additionally, the layer side of the Organic fluoride compounds of the glass of comparative example 1 after wipe test measures contact angle, result
The contact angle of water is 18 °.It can thus be appreciated that the glass of comparative example 1 reduces due to wipe test, the effect of its water repellency, not performance
Go out good hydrophobicity.
In the hurdle of the comparative example 1 of aforesaid table 1, by manufacturing condition and the glass of comparative example 1 of the glass of comparative example 1
Evaluating characteristics result collect and illustrate.
As mentioned above, it is thus identified that the stabilization of embodiment 1～3 maintains low reflexive and water repellency.
(surface analysis)
Then, in order to study the apparent condition of the glass substrate after etch processes, analysis has been made by following method
Use sample.
First, the glass substrate (soda-lime glass) to thickness 3mm implements to use the etch processes of HF gas.Etch processes
In, use the processing means 100 shown in aforesaid Fig. 2.
In processing means 100, in the 1st slit 115, the flow velocity with the 34cm/ second supplies hydrogen fluoride gas and the mixing of nitrogen
Gas.The quantity delivered of hydrogen fluoride gas is 0.7SLM (volume (liter) of the gas of internal standard state per minute), the supply of nitrogen
Amount is 31.3SLM (volume (liter) of the gas of internal standard state per minute).Additionally, mixed gas is with the shape being heated to 150 DEG C
State supplies.
Additionally, the flow velocity with the 34cm/ second supplies nitrogen in the 2nd slit 120.The temperature of nitrogen is 150 DEG C, the confession of nitrogen
Give amount for 10SLM.
Hydrogen fluoride gas is 2.4 volume % relative to the concentration of aggregate supply gas.
The capacity discharged from the 3rd slit 125 is supplied with 2 times of quantity delivered of gas.
The transporting velocity of glass substrate is 2m/ minute, and glass substrate is carried when being heated to 560 DEG C.It addition,
The temperature of glass substrate be will supply place's process gases before, use the value that records of radiation thermometer.
Etch processes time (in Fig. 2, the glass substrate time by distance S) is about 10 seconds.
By this etch processes, obtain assay sample.
Then, assay sample is used to be etched the analysis in process face.In analysis, use sweep type x-ray photoelectron
Light-dividing device (Quantera μ ESCA: A Er Wacker process Co., Ltd. (ア Le バ Star Network ワ ァ イ society) system).Analyze employing narrow
Scanning analysis (logical energy (Japanese: パ ス エ ネ Le ギ) 112eV), step can be set to 0.1eV.Additionally, in order to compare, right
The same glass substrate sample (hereinafter referred to as " comparative sample ") not implementing etch processes also implements same analysis.
It is shown in table 2 below by collecting for the analysis result obtained by assay sample and comparative sample.
[table 2]
Knowable to the analysis result of table 2: assay sample is compared with comparative sample, and the Si element on its surface is (with reference to Si2p
Hurdle) and the concentration of O element (with reference to the hurdle of O1s) reduce.Thus can confirm that the glass substrate carried out by process gases at employing
Etch processes, process the concentration of silicon oxide on surface compared with main body, significantly decrease.That is, there is the glass of antireflection
In glass, in the main body of the surface element of the glass after etch processes and the impact that is not affected by etch processes, its respective silicon oxide is dense
Degree difference.
Its result is can to form, in surface portion, the layer that refractive index is low, Funing tablet is high, is conducive to improving low reflexive.
Additionally, due to the Funing tablet of skin section is high, so improving with the affinity of Organic fluoride compounds, adaptation carries
High.
Probability is utilized in industry
The present invention may use the glass such as with high light transmission, such as building materials glass, automotive glass,
Display glass, optical element, glass used for solar batteries, glazing plate, optical glass and lens etc..
This application claims priority based on the Japanese patent application 2012-229518 proposed on October 17th, 2012,
The full content of this Japanese patent application is referenced to the application as reference.
Symbol description
100 processing meanss
110 ejectors
115 the 1st slits
120 the 2nd slits
125 the 3rd slits
150 handling unit
180 glass substrates
The glass of 300 one embodiment of the invention
310 glass substrates
312 surfaces
320 close binders
The layer of 330 Organic fluoride compounds
Claims (14)
1. there is the manufacture method of the glass of antireflection, it is characterised in that including:
A (), under normal pressure, air atmosphere, within the temperature range of 250 DEG C～650 DEG C, makes the place's process gases comprising fluorine compounds
The step contacted with the surface of glass substrate；And
B () forms the step of the layer of organic fluoride compound on described surface；
As the raw material of described place process gases, comprise fluohydric acid gas and/or trifluoroacetic acid.
2. manufacture method as claimed in claim 1, it is characterised in that the layer of described Organic fluoride compounds is processed by coating
It is formed on described surface.
3. manufacture method as claimed in claim 1 or 2, it is characterised in that the layer bag fluorinated of described Organic fluoride compounds
Polymer and/or fluorine containing silane coupling agent.
4. manufacture method as claimed in claim 1 or 2, it is characterised in that comprise hydrogen fluoride gas in described place process gases, should
The concentration of hydrogen fluoride gas is 0.1 volume %～the scope of 10 volume %.
5. manufacture method as claimed in claim 1 or 2, it is characterised in that described place process gases also comprises nitrogen and/or argon.
6. manufacture method as claimed in claim 1 or 2, it is characterised in that in the step of described (a), described glass substrate exists
Contact with described place process gases under the state being handled upside down.
7. manufacture method as claimed in claim 1 or 2, it is characterised in that in the step of described (a), at described glass substrate
Top configuration ejector, described place process gases is sprayed towards described glass substrate from described ejector.
8. manufacture method as claimed in claim 7, it is characterised in that described glass substrate by the time of described ejector is
Between 1 second～120 seconds.
9. manufacture method as claimed in claim 1 or 2, it is characterised in that the layer of described Organic fluoride compounds connects with water
Feeler is more than 90 °.
10. manufacture method as claimed in claim 1 or 2, it is characterised in that between described (a) and the step of (b), have
The step of close binder is formed on described surface.
11. glass with antireflection, it is characterised in that including:
There is the glass substrate on the high surface of Funing tablet compared with main body, and the Organic fluoride compounds formed on said surface
Layer；
The described surface of described glass substrate has nano level concavo-convex；
The described surface of described glass substrate has compared with main body silica concentration and declines, compared with main body beyond silicon
The more part of composition.
12. glass as claimed in claim 11, it is characterised in that at described glass substrate and described Organic fluoride compounds
Also there is between Ceng close binder.
13. glass as described in claim 11 or 12, it is characterised in that the layer of described Organic fluoride compounds comprises fluorine and birdss of the same feather flock together
Compound and/or fluorine containing silane coupling agent.
14. glass as described in claim 11 or 12, it is characterised in that the thickness of slab of described glass substrate is at below 3mm, and is somebody's turn to do
The meansigma methods of the absorbance in the range of the absorbance of glass substrate, i.e. wavelength 400nm～700nm is more than 88%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-229518 | 2012-10-17 | ||
| JP2012229518 | 2012-10-17 | ||
| PCT/JP2013/077845 WO2014061615A1 (en) | 2012-10-17 | 2013-10-11 | Production method for glass having anti-reflective properties, and glass having anti-reflective properties |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104718465A CN104718465A (en) | 2015-06-17 |
| CN104718465B true CN104718465B (en) | 2016-11-30 |
Family
ID=
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|---|---|---|---|---|
| JPH04249146A (en) * | 1991-02-05 | 1992-09-04 | Matsushita Electric Ind Co Ltd | Water-repellent oil-repellent stainproof film and manufacture thereof |
| JPH07300346A (en) * | 1994-05-09 | 1995-11-14 | Nippon Sheet Glass Co Ltd | Antifouling low-reflectance glass and its production |
| US6284377B1 (en) * | 1999-05-03 | 2001-09-04 | Guardian Industries Corporation | Hydrophobic coating including DLC on substrate |
| EP2371776A1 (en) * | 2010-03-30 | 2011-10-05 | Linde Aktiengesellschaft | Method for producing flat glass |
| CN102448904A (en) * | 2009-03-31 | 2012-05-09 | 康宁股份有限公司 | Glass having anti-glare surface and method of making |
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04249146A (en) * | 1991-02-05 | 1992-09-04 | Matsushita Electric Ind Co Ltd | Water-repellent oil-repellent stainproof film and manufacture thereof |
| JPH07300346A (en) * | 1994-05-09 | 1995-11-14 | Nippon Sheet Glass Co Ltd | Antifouling low-reflectance glass and its production |
| US6284377B1 (en) * | 1999-05-03 | 2001-09-04 | Guardian Industries Corporation | Hydrophobic coating including DLC on substrate |
| CN102448904A (en) * | 2009-03-31 | 2012-05-09 | 康宁股份有限公司 | Glass having anti-glare surface and method of making |
| EP2371776A1 (en) * | 2010-03-30 | 2011-10-05 | Linde Aktiengesellschaft | Method for producing flat glass |
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Granted publication date: 20161130 Termination date: 20201011 |