CN110395903A - Glass substrate - Google Patents
Glass substrate Download PDFInfo
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- CN110395903A CN110395903A CN201910328449.3A CN201910328449A CN110395903A CN 110395903 A CN110395903 A CN 110395903A CN 201910328449 A CN201910328449 A CN 201910328449A CN 110395903 A CN110395903 A CN 110395903A
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- Prior art keywords
- glass
- glass substrate
- porous layer
- inorganic porous
- tape
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- 239000011521 glass Substances 0.000 title claims abstract description 256
- 239000000758 substrate Substances 0.000 title claims abstract description 120
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 20
- 239000011737 fluorine Substances 0.000 claims abstract description 14
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000005329 float glass Substances 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 102
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 34
- 238000004519 manufacturing process Methods 0.000 description 32
- 239000007789 gas Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 19
- 238000000137 annealing Methods 0.000 description 15
- 238000004140 cleaning Methods 0.000 description 15
- 125000004429 atom Chemical group 0.000 description 14
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 12
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 230000001681 protective effect Effects 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 6
- 238000006124 Pilkington process Methods 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000002457 bidirectional effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000010583 slow cooling Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000002000 scavenging effect Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003280 down draw process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010019114 Hand fracture Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910020239 KAlF4 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004014 SiF4 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000005385 borate glass Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 239000006058 strengthened glass Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B11/00—Cleaning flexible or delicate articles by methods or apparatus specially adapted thereto
- B08B11/04—Cleaning flexible or delicate articles by methods or apparatus specially adapted thereto specially adapted for plate glass, e.g. prior to manufacture of windshields
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B18/00—Shaping glass in contact with the surface of a liquid
- C03B18/02—Forming sheets
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B18/00—Shaping glass in contact with the surface of a liquid
- C03B18/02—Forming sheets
- C03B18/18—Controlling or regulating the temperature of the float bath; Composition or purification of the float bath
-
- 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
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The present invention relates to glass substrates.The purpose of the present invention is to provide a kind of glass substrate, marresistance, impact resistance, heat resistance and cutting are excellent, and have formation on the glass substrate and the inorganic porous layer easy from the removing on glass substrate.The present invention relates to a kind of glass substrates, at least have the inorganic porous layer that fluorine (F) amount within the scope of depth 10nm~50nm is 10 atom % or more in single side.
Description
Technical field
The present invention relates to glass substrates.
Background technique
In the panel display apparatus such as digital camera, smart phone or tablet computer terminal, in order to protect display and mention
Height is beautiful and proceeds as follows: being matched thin plate protection glass in a manner of forming region more broader than image displaying part
It sets in the front of display.
According to the requirement of lightweight and slimming to panel display apparatus, it is desirable that protection glass itself is also thinning.In addition,
Excellent appearance and intensity are required panel display apparatus, in order to meet the purpose, marresistance and resistance to is required to protection glass
The raising of impact.
In order to improve the marresistance and impact resistance of glass, include the organic matters such as resin using stacking on the glass substrate
Protective layer method.For example, Patent Document 1 discloses a kind of chemically reinforced glass laminated resin bodies, which is characterized in that institute
Stating chemically reinforced glass laminated resin body includes: the layer that is made of sheet glass, the layer being made of resin layer and by above-mentioned sheet glass
With the adhesive layer of above-mentioned resin layer gluing, and the sheet glass has the chemistry that depth is 1 μm~20 μm of compressive stress layer strong
Change glass.
On the other hand, when manufacturing glass plate, by multiple conveying rollers be continuously conveyed by float glass process or glass tube down-drawing etc. at
It is slowly cooled down while the glass tape of shape.Glass tape is continuously being conveyed by the multiple conveying rollers for constituting transport path
It is slowly cooled and solidifies simultaneously, and be cut into defined length, thus obtain glass substrate.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2015-101044 bulletin
Summary of the invention
Problem to be solved by the invention
In the manufacturing process of glass substrate, when generating scratch (wound) on the surface of the glass, stress is easy to concentrate on drawing
On trace.Contact scratch is formed especially on the face contacted with conveying roller, there are problems that strength reduction.
In addition, the production of cleaning, chemical intensification treatment, device after the manufacture of glass substrate and conveying operation etc.
In, it is also easy to generate scratch on the surface of the glass.Especially in the strengthened glass with tensile stress layer, develop in scratch etc.
In the case where tensile stress layer, there are problems that being easy self destroys.
In addition, glass substrate is immersed in the acid solutions such as hydrogen fluoride (HF) aqueous solution in order to remove the scratch of glass surface
When being etched in, there are the following problems: the scratches such as existing potential scratch (latent wound) instead can on the glass surface
Expand and visualizes.
However, resin layer, adhesive layer for recording in as equal such as patent document 1 etc., by the protective film comprising organic matter
It pastes in method on the glass substrate, the heat resistance of protective film is low, protection only is provided in the low temperature range in manufacturing process,
It is difficult to protect glass substrate in process in high temperature range.In addition, the protective film comprising organic matter is pasted on the glass substrate
It is difficult to cut together with glass substrate later, therefore needs to remove from glass substrate before the cutting of glass substrate.In addition,
In order to which the protective film that will include organic matter is pasted on the glass substrate, need the process of the protective film and glass substrate gluing,
It is from glass substrate that protective film removing is not easy.
The present invention is to complete in view of the above problems, and the present invention provides a kind of glass substrate, marresistance, impact resistance
Property, heat resistance and cutting it is excellent, and have convenient for being formed on the glass substrate and convenient for removing from glass substrate
Inorganic porous layer.
The means used to solve the problem
The inventors of the present invention's discovery, by the inorganic porous layer with Funing tablet in particular range, can be improved glass base
Marresistance, impact resistance, heat resistance and the cutting of plate, and the inorganic porous layer is convenient for removing from glass substrate, and
The present invention is completed based on the discovery.
That is, the present invention is as described below.
[1] a kind of glass substrate, wherein the glass substrate at least has within the scope of depth 10nm~50nm in single side
The inorganic porous layer that fluorine (F) amount is 10 atom % or more.
[2] glass substrate as described in [1], wherein the inorganic porous layer with a thickness of 200nm or more.
[3] glass substrate as described in [1] or [2], wherein include crystalline phase in the inorganic porous layer.
[4] glass substrate as described in any one of [1]~[3], wherein the porosity of the inorganic porous layer is 30%
More than.
[5] glass substrate as described in any one of [1]~[4], wherein the glass substrate is float glass.
Invention effect
Glass substrate according to the present invention, by the inorganic porous layer with Funing tablet in particular range, inorganic more
In the forming face of aperture layer, scratch the reason of becoming the strength reduction generated in the manufacturing process for causing glass substrate is removed,
Or changed to be not easy to drop low intensive shape, therefore be able to suppress the strength reduction of glass substrate.
In addition, the scratch of glass surface is removed or the shape of scratch occurs in the forming face of inorganic porous layer
Variation, therefore can prevent from being etched by being immersed in glass substrate in the acid solutions such as the aqueous solution containing hydrogen fluoride (HF)
It handles and the scratch is expanded and is visualized.In addition, this is inorganic more after the manufacturing process of glass substrate and manufacture in process
Aperture layer also works as protective film, therefore marresistance and excellent impact resistance.
Inorganic porous layer excellent heat resistance can protect glass in the process in high temperature range.In addition, due to
Cutting and chamfering process can be carried out in the state of by the attachment of inorganic porous layer on the glass substrate, therefore cut with having pasted
The glass substrate for cutting the existing protective film comprising organic matter for losing defencive function after process and cutting action is compared, and is prevented
The excellent effect of scratch can prevent the reduction of intensity.Therefore, it by forming inorganic porous layer on the glass substrate, does not need
Further the protective film comprising organic matter is pasted on the glass substrate, is also excellent from the viewpoint of industry.
The means of inorganic porous layer are formed on the glass substrate and the means of the inorganic porous layer are removed from glass substrate
It is easy and at low cost, also, the glass compared with forming the glass substrate before the inorganic porous layer, after removing the inorganic porous layer
Substrate has the advantages that intensity is high.
Detailed description of the invention
Fig. 1 is the explanatory diagram of an example of the manufacturing method of the glass substrate of embodiments of the present invention, to indicate float glass process glass
The cross-sectional view of the outline of glass manufacturing device.
Fig. 2 is the figure for schematically showing the bidirectional flow type injector 70 of embodiments of the present invention.
Fig. 3 is the figure for schematically showing the uniflow type injector 80 of embodiments of the present invention.
Fig. 4 is the XPS analysis for indicating the fluorine atom concentration distribution of the depth relative to glass substrate of glass substrate of example 3
As a result.
Fig. 5 is the SEM image for indicating the effective cross-section of glass substrate of example 5.
The XRD spectrum of 3 glass substrate for Fig. 6.
Appended drawing reference
12: melten glass
14: glass tape
14b: bottom surface
70,80: injector
71,81: supply mouth
74,84: flow path
75,85: exhaust outlet
100: float glass manufacturing device
200: melting appartus
300: forming device
310: molten tin
320: bath
400: annealing device
Specific embodiment
[glass substrate]
Hereinafter, the glass substrate to embodiments of the present invention is illustrated.The glass substrate of embodiments of the present invention
At least there is the inorganic porous layer that fluorine (F) amount within the scope of depth 10nm~50nm is 10 atom % or more in single side.It is inorganic more
Aperture layer refers to the layer for foring many holes (aperture) comprising inorganic matter.
F amount within the scope of depth 10nm~50nm of inorganic porous layer be 10 atom % or more, preferably 30 atom % with
Upper, more preferably 50 atom % or more.By the way that the F amount within the scope of depth 10nm~50nm is adjusted to 10 atom % or more, nothing
Machine porous layer works as protective film, and since fluorine is ion-bonded, dissolubility height, easy by liquid
In processing and remove.From the viewpoint of the mechanical strength of inorganic porous layer, F amount within the scope of depth 10nm~50nm it is upper
Limit is preferably generally 90 atom % or less, more preferably 80 atom % or less, further preferably 70 atom % or less.
F amount within the scope of depth 10nm~50nm of inorganic porous layer is found out in the following way: utilizing x-ray photoelectron
The energy disperse spectroscopy Quantera II of manufacture (ULVAC-PHI company) measure respectively the depth apart from glass baseplate surface be 10nm,
F amount at 18nm, 26nm, 34nm, 42nm and 50nm, and calculate its average value.
Depth apart from glass baseplate surface is that the amount of the atom in the inorganic porous layer within the scope of 10nm~50nm passes through
As under type is found out: using the x-ray photoelectron spectroscopy Quantera II of manufacture (ULVAC-PHI company) measure respectively away from
Depth from glass baseplate surface is the amount of the atom at 10nm, 18nm, 26nm, 34nm, 42nm and 50nm, and it is average to calculate it
Value.Grinding from glass baseplate surface to 100 μm of depth can for example carry out in the following way: utilize cerium oxide aqueous solution
100 μm of depth are ground to, C is then utilized60Ion beam carries out sputter etching.
Inorganic porous layer and glass have chemical bonding, without specific boundary, form consecutive variations.F amount is in depth
Highest near 10nm, concentration is kept constant from depth 10nm, is then obliquely reduced along depth direction.With phase at depth 10nm
Than in outmost surface~10nm depth bounds, due to the carbon of ion exchange and surface contamination with the water in air
In the presence of F concentration is low.Glass base about the composition of inorganic porous layer, preferably by being formed with the inorganic porous layer on the surface thereof
Reduce the amount of silicon (Si) and oxygen (O) in the main body composition of plate and the composition for having imported fluorine (F) is constituted.As inorganic porous
For the composition of layer, such as the composition comprising F, Na, Al, Mg can be enumerated.
The thickness of inorganic porous layer be preferably 200nm or more, more preferably 350nm or more, further preferably 500nm with
On.By inorganic porous layer with a thickness of 50nm or more, can almost remove and being contacted with conveying roller on glass
The scratch of generation, and it is able to suppress the scratch generated because contacting with conveying roller.Inorganic porous layer with a thickness of 100nm or more
When, it some times happens that the scattering or glittering (ギ ラ Star キ) etc. of visible light, can be removed inorganic more by aftermentioned removal step
Aperture layer.In addition, the thickness of inorganic porous layer is preferred from the viewpoint of the surface roughness of the glass after removing inorganic porous layer
For 1500nm or less, more preferably 1000nm or less, further preferably 500nm or less.
Inorganic porous layer preferably comprises crystalline phase.By the inclusion of crystalline phase, the mechanical strength of inorganic porous layer improves, is wear-resisting
Damage property improves.For the structure of crystalline phase, such as Na can be enumerated2MgAlF7。
The presence of crystalline phase for example can measure (XRD) etc. by powder x-ray diffraction to confirm.
The quantity in the hole in inorganic porous layer is not particularly limited, and examines from the viewpoint of impact absorbency (rushing attack retentivity)
Consider, the ratio (porosity) in the hole formed in inorganic porous layer is preferably 30% or more, is more preferably 40% or more, is further excellent
It is selected as 50% or more.In addition, from the viewpoint of the mechanical strength of inorganic porous layer, porosity is preferably 80% or less, more excellent
It is selected as 70% or less, further preferably 60% or less.The porosity of inorganic porous layer is calculated by following formula.
ρP=ρG-(ΔM/d·S) (1)
α={ 1- (ρP/ρF)}×100 (2)
Here, α indicates porosity (%), ρPIndicate the density of inorganic porous layer, ρGIndicate the density of glass substrate, ρFTable
Show the averag density for constituting the crystalline component of inorganic porous layer, Δ M indicates that (hole formation is handled before and after the processing using hydrogen fluoride gas
Front and back) glass weight difference, d indicates the thickness of inorganic porous layer, the area of S indicates that treated glass.
Each hole in inorganic porous layer is aperture, and the surface of the inorganic porous layer is in there are the states of minute asperities.It can
To speculate: by the way that there are such minute asperities, contact area is reduced, and scratch resistance improves.
From the viewpoint of protecting glass substrate from processes such as processing after the manufacturing process of glass substrate and manufacture, nothing
Machine porous layer has more than a certain amount of thickness preferably as described above, but considers from viewpoint in practical use, preferably by glass substrate
Inorganic porous layer is finally removed whens for protecting glass etc. from glass substrate.
For the method for removing inorganic porous layer from glass substrate, such as it can enumerate in containing water and acid
The method impregnated in the cleaning solution of at least one.For acid, such as hydrochloric acid, nitric acid, hydrofluoric acid and sulfuric acid can be enumerated.Its
In, since hydrofluoric acid can not only remove inorganic porous layer, additionally it is possible to etch glass surface, inorganic porous layer and glass can be made
Interface smoothing, to improve the flatness of the glass surface after removing inorganic porous layer, therefore preferred hydrofluoric acid.
In order to remove inorganic porous layer in a short time, ultrasonic wave also can be used.It can be by glass substrate
The injection of cleaned face be previously applied ultrasonic wave cleaning solution ultrasonic cleaning or glass substrate is impregnated in be applied with
Ultrasonic cleaning in the cleaning solution of ultrasonic wave and remove inorganic porous layer.In addition, passing through the glass that will form inorganic porous layer
Glass substrate is immersed in the mixed melting salt for chemical intensification treatment, can carry out removing from glass substrate simultaneously inorganic more
The chemical intensification treatment of aperture layer and glass.
In the case where using water to remove inorganic porous layer as cleaning solution, larger change occurs according to water temperature for removal efficiency
Change.40 DEG C or more of water can be used for example and remove inorganic porous layer.Alternatively, it is also possible to use the steam of high temperature.
The temperature of cleaning solution, scavenging period are preferably suitably adjusted according to the thickness of inorganic porous layer, composition of cleaning solution etc..
About the temperature of cleaning solution, such as using water as in the case where cleaning solution, it is usually preferred to be set as 30 DEG C~50 DEG C, more preferably
It is set as 40 DEG C~50 DEG C.In addition, scavenging period be generally preferably set as 20 minutes or more, more preferably be set as 40 minutes with
On.In addition, the temperature of cleaning solution is preferred in the case that the acid solution such as in the hydrochloric acid or hydrofluoric acid that use 1M is as cleaning solution
It is set as 10 DEG C~25 DEG C, scavenging period is preferably set to 1 minute~10 minutes.
In glass after removing inorganic porous layer, depth is that the scratch of 100nm or more is preferably 40000/m2Below, more
Preferably 20000/m2It below, is more preferably 4000/m2Below.The scratch that depth in glass is 100nm or more
Quantity can be surveyed after opening scratch using about 1 μm of hydrofluoric acid etch using the QV STREAM PLUS of three rich company's manufactures
It is fixed.
In glass after removing inorganic porous layer, the average surface roughness of the glass surface of the side with inorganic porous layer
Degree Ra is preferably 5nm or less, more preferably 3.5nm or less, further preferably 1nm or less.Pass through average surface roughness Ra
For 5nm hereinafter, the intensity after removing inorganic porous layer is high.The average surface roughness Ra of glass surface passes through according to JIS
The method of B0601-2013 is measured.
For the glass substrate of present embodiment, it can be formed, be can be used by float glass process or glass tube down-drawing etc.
The glass substrate of various compositions.Specifically, can for example enumerate comprising alumina silicate glass, soda-lime glass, borate glass,
Lithium alumina silicate glass, alkali-free glass, borosilicate glass and various other glass transparency glass plate.For by float glass process at
In the case where the float glass of shape, there is above-mentioned inorganic porous layer preferably on at least bottom surface of float glass.
The plate thickness of glass substrate is not particularly limited, due to plate thickness with square form work to intensity, in plate
In the case that thickness is relatively thin, intensity is easily become a problem.Thus, for example it is preferred that in the following order: 0.7mm or less, 0.5mm or less,
0.3mm or less, 0.1mm or less.In addition, being 0.3mm or more for typical case.
[manufacturing method of glass substrate]
Then, the manufacturing method of glass substrate of the invention is illustrated.The manufacturing method of glass substrate of the invention
The process for forming inorganic porous layer comprising supplying the gas containing fluorine or fluoride at least one side of glass.As fluoride
For, preferred fluorinated hydrogen.
By to the gas of at least one side of glass supply hydrogen fluoride (HF) etc. containing fluorine atom, the main body composition of glass at
For fluoride, in the case where the fusing point of the fluoride is lower than the temperature handled glass, fluoride gasification volatilization.Example
Silicon (Si), potassium (K), oxygen (O) ingredient in such as glass are bonded with fluorine (F) and become SiF4、KAlF4、H2The concurrent angerization such as O
And it is detached from from glass surface.At this point, the thickness of glass entirety is constant, thus it is speculated that generated by mentioned component from glass surface volatilization
Hole, therefore form the porous structure of aperture.
From preventing to from the viewpoint of the corrosion of the equipment such as the injector of glass supply gas, hydrogen fluoride (HF) etc. contains fluorine
It is preferable to use nitrogen (N for the gas of atom2) or the non-active gas such as rare gas as carrier gas and with the mixing with these carrier gas
The form of gas is supplied to ribbon surfaces.
The temperature of glass when supplying the gas containing fluorine atom such as hydrogen fluoride (HF) is preferably 30 DEG C or more, is more preferably
200 DEG C or more, further preferably 300 DEG C or more.Additionally, it is preferred that being 750 DEG C or less, more preferably 700 DEG C or less, further
Preferably 650 DEG C or less.By the way that the temperature of above-mentioned glass is set as 30 DEG C or more, can be formed in the not liquefied situation of HF
Inorganic porous layer.In addition, the temperature of glass is higher in basic principle, the formation of the inorganic porous layer corresponding to same HF amount
Efficiency more improves, therefore the treatment temperature the high the more preferred.On the other hand, by by the temperature of above-mentioned glass be set as 750 DEG C with
Under, thus forming the eutectic melting point of the fluoride of inorganic porous layer hereinafter, can prevent layer from melting.
The thickness (d) of inorganic porous layer by the gas containing hydrogen fluoride supply conditions (HF concentration (c) and time of contact
(t)) it determines, can be indicated by following formula.Here, α ' is the proportionality constant determined by treatment temperature.
D=α ' × c × t (3)
Then, an example as the manufacturing method of the glass substrate of embodiments of the present invention, manufactures glass to by float glass process
The example of glass substrate is illustrated.Fig. 1 is the explanatory diagram of the manufacturing method of the glass substrate of embodiments of the present invention, to indicate
The cross-sectional view of the outline of float glass manufacturing device.
Float glass manufacturing device 100 include fusing glass raw material 10 and obtain melten glass 12 melting appartus 200,
By the melten glass 12 supplied from melting appartus 200 be configured to forming device 300 that is band-like and obtaining glass tape 14 and at
Shape dress sets the annealing device 400 that the glass tape 14 after shaping in 300 carries out slow cooling.
Melting appartus 200 includes the melting glass for accommodating the melting tank 210 of melten glass 12 and accommodating in melting tank 210
The top of glass 12 forms the burner 220 of flame.The glass raw material 10 put into melting tank 210 passes through from burner 220
The flame radiation of formation is hot and gradually fuses as melten glass 12.Melten glass 12 is continuously fed into forming from melting tank 210
Device 300.
Forming device 300 has the bath 320 for accommodating molten tin 310.In forming device 300, it is continuously fed by making
Melten glass 12 in molten tin 310 in molten tin 310 along prescribed direction flow and be configured to it is band-like, to obtain glass tape
14。
Atmosphere temperature in forming device 300 is lower closer to exporting from the entrance of forming device 300.Forming device
Atmosphere temperature in 300 passes through heater (not shown) being arranged in forming device 300 etc. and adjusts.
Glass tape 14 while being flowed along prescribed direction be cooled, bath 320 downstream area by glass tape 14 from
Lift in molten tin 310.The glass tape 14 lifted from molten tin 310 is delivered to annealing device 400 by runner 510.
Annealing device 400 carries out slow cooling to the glass tape 14 after shaping in forming device 300.Annealing device 400 is for example
Include: the leer (annealing furnace) 410 of heat insulation structural is arranged in leer 410 and conveys glass tape 14 along prescribed direction
Multiple conveying rollers 420.Atmosphere temperature in leer 410 is lower closer to exporting from the entrance of leer 410.
Atmosphere temperature in leer 410 passes through the heater 440 being arranged in leer 410 and waits adjusting.Utilize cutting
The glass tape 14 transported from the outlet of leer 410 is cut into predetermined size by machine, and is delivered as product.
Before delivering as product, grinding can according to need, cleaning glass substrate does not form inorganic porous layer
Surface., can be in the case where although the surface grinding to glass substrate is primary but is unsatisfactory for the quality requirements such as flatness
The surface of glass substrate is regrind.
Glass substrate cleaning for example by spray cleaning, used disc brush slurry clean or be sprayed into
Row.In slurry cleaning, by supplying slurry (such as cerium oxide aqueous solution and calcium carbonate aqueous solution) to the surface of glass substrate
While ground with disc brush, to remove the remaining slurry residues of glass surface.
In the manufacturing method of the glass substrate of embodiments of the present invention, as shown in Figure 1, using being arranged in annealing device
The injector 70,80 of the lower section of glass tape 14 in 400 contains the gas of hydrogen fluoride (HF) to the supply of the bottom surface of glass tape 14,
Thus inorganic porous layer is formed in the bottom surface of glass tape 14.
The manufacturing method of the substrate of embodiments of the present invention is not limited to above embodiment etc., such as also can be used and set
It sets in the top of the glass tape 14 in annealing device 400 or the injector 70,80 above and below being separately positioned on.
Fig. 2 is the figure for schematically showing the bidirectional flow type injector 70 of embodiments of the present invention.Fig. 3 is schematic
The figure of the uniflow type injector 80 of embodiments of the present invention is shown.
Gas from the blowing of the supply mouth 71,81 of injector 70,80 to the bottom surface 14b of glass tape 14 is relative to glass tape
14 moving direction flows out to move on flow path 74,84 forward or backwards to exhaust outlet 75,85.
Injector 70,80 can be used with arbitrary form, can also on the moving direction of glass tape 14 arranged in series 2
Ribbon surfaces are handled above.
Bidirectional flow type injector 70 is illustrated in figure 2 the mobile phase from supply mouth 71 to the gas of exhaust outlet 75 for glass
The moving direction of glass band 14 is in positive (arrow 74) injector with reversed impartial distribution.
Uniflow type injector 80 is the mobile phase from supply mouth 81 to the gas of exhaust outlet 85 for glass tape 14
Moving direction is fixed as the injector in any one direction in forward or backwards.In the embodiment of fig. 3, from supply mouth 81
Mobile phase to the gas of exhaust outlet 85 is positive (arrow 84) for the moving direction of glass tape 14.
The supply mouth 71,81 of injector 70,80 and the bottom surface 14b distance D of glass tape 14 are preferably 5mm~50mm, more
Preferably 8mm or more.In addition, distance D is more preferably 30mm or less, further preferably 20mm or less.
By the way that distance D is set as 5mm or more, such as even if can also be kept away since earthquake etc. causes glass tape 14 to vibrate
Exempt from the bottom surface 14b of glass tape 14 and the contact of injector 70,80.In addition, by the way that distance D is set as 50mm hereinafter, can press down
Gas processed is spread in the inside of forming device 300 or annealing device 400, relative to desired gas flow, can make sufficient amount
Gas reach glass tape 14 bottom surface 14b.
The distance L on the moving direction of glass tape 14 of injector 70,80 is preferably 100mm~500mm, is more preferably
150mm or more, further preferably 200mm or more.In addition, distance L is more preferably 450mm or less, further preferably 400mm
Below.
By the way that distance L is set as 100mm or more, supply mouth 71,81 and exhaust outlet 75,85 can be set.It is preferably bidirectional
The distance L of flow-type injector 70 is 150mm or more, the distance L of uniflow type injector 80 is 100mm or more.In addition, logical
It crosses and distance L is set as 500mm hereinafter, being able to suppress the injector by being arranged in forming device 300 or annealing device 400
70, the thermal loss (desuperheating amount) of glass tape 14 caused by 80, therefore it is able to suppress the output power of multiple heaters.
About the distance in the width direction of glass tape 14 of injector 70,80, preferably with glass tape 14 at this
Distance more than product area on direction.Preferably 3000mm or more, more preferably 4000mm or more.
In addition, supply containing hydrogen fluoride (HF) gas supply mouth 71,81 and exhaust outlet 75,85 preferably with glass tape 14
Bottom surface 14b it is opposite.Supply mouth 71,81 and exhaust outlet 75,85 are in injector 70,80 in the width direction of glass tape 14
There is shape of slit in the range of whole region.
In addition, the temperature of glass tape 14 is usually 200 DEG C~600 DEG C in annealing device 400.The temperature of glass tape 14 is
At 200 DEG C or more, it is able to maintain that the effect that the formation of the inorganic porous layer of ribbon surfaces carries out.In addition, the temperature of glass tape 14
When degree is 600 DEG C or less, it is able to suppress the heat of the glass tape 14 as caused by the injector 70,80 being arranged in annealing device 400
Amount loss (desuperheating amount), therefore it is able to suppress the output power of multiple heaters.
Hydrogen fluoride (HF) concentration c (volume %) is preferably 0.1%~50%, more preferably 1% or more, further preferably
2% or more.In addition, concentration c is more preferably 40% or less, further preferably 30% or less.When concentration c is 0.1% or more, energy
It is enough that inorganic porous layer is formed in the case where not significantly increasing distance L.In addition, by the way that concentration c is set as 50% hereinafter, can
Mitigate the corrosion of injector.
Time of contact t is preferably 1 second~300 seconds, more preferably 2 seconds or more, further preferably 3 seconds or more.When contact
Between t be more preferably 180 seconds or less, further preferably 60 seconds or less.Time of contact t by injector distance L and glass tape
Conveying speed determines, by the way that time of contact t is set as 1 second or more, supply mouth 71,81 and exhaust can be arranged on the injector
Mouth 75,85, therefore, can be realized the stable operation of technique.In addition, by the way that time of contact t is set as 180 seconds hereinafter, spraying
The distance L of device becomes smaller, therefore is able to suppress the thermal loss (desuperheating amount) of the glass tape 14 as caused by injector 70,80, can
Inhibit the output power of multiple heaters.
Inorganic porous layer is respectively as a proportion with concentration c and time of contact t as described above, therefore by according to production line
Concentration c appropriate and time of contact t are selected, the inorganic porous layer of any thickness is capable of forming.
According to the above, passing through the bottom surface of adjustable range D, distance L, glass tape 14 into conveying in above-mentioned preferred scope
14b supply contain hydrogen fluoride (HF) gas when glass tape 14 temperature, the concentration c or time of contact t of hydrogen fluoride (HF),
The thickness of fluorine (F) amount and inorganic porous layer in inorganic porous layer can be controlled.
More than, to the gas for containing hydrogen fluoride (HF) in the process for manufacturing glass substrate by float glass process, to glass tape supply
The example of body is illustrated, but not limited to this.For example, it is also possible to contain fluorination to glass substrate supply in closed container etc.
The gas of hydrogen (HF).
[embodiment]
Hereinafter, the embodiment of the present invention and comparative example are concretely demonstrated.It should be noted that the present invention is not limited to
These are recorded.
(example 1)
So that the mode that the group of obtained glass substrate becomes following compositions prepares glass raw material 10, and glass is former
In 10 investment melting appartus 200 of material.(composition) is indicated with the quality percentage of oxide benchmark, contains 61% SiO2, 11%
Al2O3, 12% Na2O, 6% K2O, 7% MgO, 2% ZrO2。
Glass raw material 10 is melted in melting appartus 200 and obtains melten glass 12, is then supplied to melten glass 12
In forming device 300, melten glass 12 is configured to it is band-like, to obtain glass tape 14.It is drawn from the outlet of forming device 300
Then glass tape 14 out have carried out slow cooling in annealing device 400.
At the position that the temperature of the glass tape 14 in annealing device 400 is 450 DEG C (treatment temperature), it is provided with glass tape
The distance L of 14 moving direction is the injector 70 of 300mm.By the bottom surface 14b of the supply mouth 71 of injector 70 and glass tape 14
The distance between D be set as 10mm.
Fluorine is blown to the bottom surface 14b of glass tape 14 for 50cm/s with flow velocity (linear velocity) u from the supply mouth 71 of injector 70
Changing hydrogen (HF) concentration c is 10 volume % with nitrogen (N2) it is the gas of carrier gas, so as to form inorganic porous layer.By hydrogen fluoride
(HF) time of contact (processing time) of gas and glass tape 14 is set as 4 seconds.Glass is pulled out from the outlet of forming device 300
Then band 14 carries out slow cooling in annealing device 400, to obtain glass substrate.
(example 2~7)
In addition to treatment conditions (treatment temperature (DEG C), HF concentration (volume %), processing time (second)) are set as shown in table 1
Condition other than, glass substrate has been obtained under conditions of same as Example 1.Example 6 and example 7 using hydrogen fluoride gas without being carried out
Processing, in example 7, pasted PET (polyethylene terephthalate) film on the two sides of glass substrate.
Example 1~5 is embodiment, and example 6 and 7 is comparative example.The object of obtained glass substrate is had detected by the following method
Property.
[fluorine (F) atomic concentration (atom %) of outmost surface]
Glass substrate obtained in example 1~5 is respectively cut as width 10mm × length 10mm, x-ray photoelectron is utilized
The depth of the energy disperse spectroscopy Quantera II of manufacture (XPS, ULVAC-PHI company) measurement apart from glass baseplate surface be 10nm,
Respective F amount (atom %) at 18nm, 26nm, 34nm, 42nm and 50nm, using the average value of the F concentration of each point as depth
Fluorine amount within the scope of 10nm~50nm compares.
For the determination condition of XPS analysis, x-ray source uses the monochromatization AlK alpha ray of 100W, and photoelectron is examined
It surveys area and is set as 100 μm of φ, photoelectron detection angle is set as 45 degree, 224eV can be set as by logical, plasma sputter uses
C60Ion.From the respective peak intensity of the element detected by XPS analysis, fluorine atom concentration distribution has been used.In addition, away from
Depth from surface is based on SiO2The sputter rate of sputtered film is found out.
[porosity in inorganic porous layer]
Glass is implemented using the weight difference of the glass of hydrogen fluoride gas before and after the processing for the glass substrate of 1~example of example 5
The scanning electron microscope (SEM) in section is observed, and calculates porosity α by following formula.
ρP=ρG-(ΔM/d·S) (1)
α={ 1- (ρP/ρF)}×100 (2)
Here, α indicates porosity (%), ρPIndicate the density of inorganic porous layer, ρGIndicate the density of glass substrate, ρFTable
Show the averag density for constituting the crystalline component of inorganic porous layer, Δ M indicates to utilize the weight of the glass of hydrogen fluoride gas before and after the processing
It is poor to measure, and d indicates the thickness of inorganic porous layer, the area of S expression treated glass.
[the presence or absence of crystalline phase in inorganic porous layer]
The presence or absence of the crystalline phase in inorganic porous layer is determined by powder x-ray diffraction (XRD).
[thickness (nm) of inorganic porous layer]
By being utilized at hydrogen fluoride gas using scanning electron microscope (SU-8030 that SEM, Hitachi, Ltd manufacture) observation
Glass effective cross-section after reason, to determine the thickness of inorganic porous layer.
[marresistance]
Process face (bottom surface) for the glass substrate of 1~example of example 5, the glass substrate for example 6 it is any one side, for
The PET film adhesive surface of the glass substrate of example 7, respectively using the surface property analyzer for the pin for being mounted with SiN (the new scientific society's system in east
Make, HEIDON 14FW), the load for applying 50g is rubbed.Then, inorganic porous layer or PET film are removed, microscope is utilized
Have rated the presence or absence of scratch.Marresistance refers to that the position in micro- sem observation in friction is not present or only exists for zero
Scratch less than 3 20 μm or more, × refer to that there are 3 or more 20 μm or more of scratches in the position of friction.
[cutting]
Have rated the process face (bottom surface) of the glass substrate to 1~example of example 5, to any one side of the glass substrate of example 6, right
The PET film adhesive surface of the glass substrate of example 7 is utilized respectively glass cutter (manufacture of Samsung diamond company, GCC-P-M15P) with straight
Line production cutting line and whether generate when fractureing by hand fracture it is bad.At this point, fractureing bad refer to glass cutter system
The cutting line of work is the situation of 2mm or more at a distance from the cutting line t of the glass substrate actually ruptured.Cutting refers to this for zero
Distance be less than 2mm, × refer to the distance for 2mm or more.
[heat resistance]
The glass substrate of 1~example of example 7 is heated 10 minutes at 500 DEG C in the cabinet-type electric furnace of air atmosphere, is then examined
Whether the appearance for having looked into glass substrate changes.Heat resistance be zero refer to appearance do not change, × refer to that appearance is changed.
It shows the result in table 1 and Fig. 4~6.
"-", which refers to, in table 1 is not carried out or is not present.
Fig. 4 is the XPS analysis of the glass substrate of example 3 as a result, indicating the fluorine atom concentration of the depth relative to glass substrate
Distribution.Fig. 5 indicates the SEM image of the effective cross-section of the glass substrate of example 5, can measure porosity, the thickness of inorganic porous layer.
The XRD spectrum of 3 glass substrate for Fig. 6, is able to confirm that the presence of crystalline phase.
Table 1
For the glass substrate of example 1~5, marresistance is high compared with the glass substrate of example 6, the glass base with example 7
Plate is good compared to cutting, and heat resistance is also high.It can be seen from this result that glass substrate of the invention passes through with depth 10nm~50nm
In range fluorine (F) amount (F concentration) be 10 atom % or more inorganic porous layer, have excellent cutting, heat resistance and
Marresistance.
As described above, the manufacturing method about glass substrate and glass substrate, implements in detail and with reference to specific
Mode is illustrated, but the present invention is not limited to the above embodiments, to those skilled in the art obviously
It is that can make various changes, correct without departing from the spirit and scope of the present invention.
Industrial applicability
Glass substrate of the invention can remove glass base by the inorganic porous layer with Funing tablet in particular range
The scratch on glass substrate generated in the manufacturing process of plate, and glass substrate is protected, since contact area is small, sliding
Property good, marresistance and excellent impact resistance.In addition, due to being not easy to charge, heat resistance it is high, excellent in workability.This
Outside, from the viewpoint of industry, the formation and removing of inorganic porous layer are also easy and low cost.After removing inorganic porous layer
Glass substrate low reflection (Anti Reflection) property it is excellent and scratch is few, it is also excellent in terms of intensity.
Glass substrate of the invention is suitable for smart phone, tablet computer terminal, digital camera or solar battery etc.
Protection glass or display, particularly touch-screen display protection glass.
Although illustrating the present invention in detail and with reference to specific embodiment, show to those skilled in the art
And be clear to, it can make various changes, correct without departing from the spirit and scope of the present invention.
The application is based on Japanese patent application 2018-084142 filed on April 25th, 2018 and Shen on April 19th, 2019
Japanese patent application 2019-080025 please, by its content it is incorporated herein by reference in.
Claims (5)
1. a kind of glass substrate, wherein the glass substrate at least has the fluorine (F) within the scope of depth 10nm~50nm in single side
Amount is the inorganic porous layer of 10 atom % or more.
2. glass substrate as described in claim 1, wherein the inorganic porous layer with a thickness of 200nm or more.
3. glass substrate as claimed in claim 1 or 2, wherein include crystalline phase in the inorganic porous layer.
4. glass substrate according to any one of claims 1 to 3, wherein the porosity of the inorganic porous layer is 30%
More than.
5. glass substrate as described in any one of claims 1 to 4, wherein the glass substrate is float glass.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018-084142 | 2018-04-25 | ||
| JP2018084142 | 2018-04-25 | ||
| JP2019080025A JP7275801B2 (en) | 2018-04-25 | 2019-04-19 | glass substrate |
| JP2019-080025 | 2019-04-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110395903A true CN110395903A (en) | 2019-11-01 |
Family
ID=68322892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910328449.3A Pending CN110395903A (en) | 2018-04-25 | 2019-04-23 | Glass substrate |
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| Country | Link |
|---|---|
| CN (1) | CN110395903A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103492338A (en) * | 2011-04-15 | 2014-01-01 | 旭硝子株式会社 | Method for producing surface-treated glass substrate |
| WO2015046109A1 (en) * | 2013-09-25 | 2015-04-02 | 旭硝子株式会社 | Glass plate |
| WO2015046116A1 (en) * | 2013-09-25 | 2015-04-02 | 旭硝子株式会社 | Glass plate |
| TW201518222A (en) * | 2013-09-25 | 2015-05-16 | Asahi Glass Co Ltd | Glass plate |
| WO2017073580A1 (en) * | 2015-10-29 | 2017-05-04 | 旭硝子株式会社 | Glass substrate for displays and method for producing glass substrate for displays |
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2019
- 2019-04-23 CN CN201910328449.3A patent/CN110395903A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103492338A (en) * | 2011-04-15 | 2014-01-01 | 旭硝子株式会社 | Method for producing surface-treated glass substrate |
| WO2015046109A1 (en) * | 2013-09-25 | 2015-04-02 | 旭硝子株式会社 | Glass plate |
| WO2015046116A1 (en) * | 2013-09-25 | 2015-04-02 | 旭硝子株式会社 | Glass plate |
| TW201518222A (en) * | 2013-09-25 | 2015-05-16 | Asahi Glass Co Ltd | Glass plate |
| WO2017073580A1 (en) * | 2015-10-29 | 2017-05-04 | 旭硝子株式会社 | Glass substrate for displays and method for producing glass substrate for displays |
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