CN104334507B - Alkali-free glass substrate and the thining method of alkali-free glass substrate - Google Patents
Alkali-free glass substrate and the thining method of alkali-free glass substrate Download PDFInfo
- Publication number
- CN104334507B CN104334507B CN201380028321.6A CN201380028321A CN104334507B CN 104334507 B CN104334507 B CN 104334507B CN 201380028321 A CN201380028321 A CN 201380028321A CN 104334507 B CN104334507 B CN 104334507B
- Authority
- CN
- China
- Prior art keywords
- mgo
- free glass
- alkali
- glass substrate
- cao
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011521 glass Substances 0.000 title claims abstract description 247
- 239000000758 substrate Substances 0.000 title claims abstract description 134
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 244
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium monoxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 120
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims abstract description 56
- KRHYYFGTRYWZRS-UHFFFAOYSA-N HF Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 41
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 10
- 238000005530 etching Methods 0.000 claims description 19
- 238000011068 load Methods 0.000 claims description 14
- 208000004698 Branchiootic syndrome Diseases 0.000 claims description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 3
- 229910052904 quartz Inorganic materials 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 abstract description 3
- 238000007792 addition Methods 0.000 description 30
- 238000004031 devitrification Methods 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 238000005452 bending Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000002844 melting Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 241000282890 Sus Species 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 231100000241 scar Toxicity 0.000 description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N Antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N Tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 238000003556 assay method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000005712 crystallization Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003628 erosive Effects 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N Ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 229910020230 SIOx Inorganic materials 0.000 description 1
- 229910004207 SiNx Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Abstract
The present invention relates to a kind of alkali-free glass substrate, its for by Fluohydric acid. (HF) etch processes be thinned more than 5 μm, thickness of slab be the alkali-free glass substrate of below 0.4mm, its specific modulus is more than 32MNm/kg, photoelastic constant is below 31nm/MPa/cm, the strain point of the glass of this substrate is more than 710 DEG C, and the mean thermal expansion coefficients at 50～350 DEG C is 30 × 10‑7～43 × 10‑7/ DEG C, viscosity reaches 102Temperature T during dPa s2Being less than 1710 DEG C, viscosity reaches 104Temperature T during dPa s4Being less than 1320 DEG C, the composition of this glass contains in terms of based on oxide mole of %: SiO266～70, Al2O312～15, B2O30～1.5, MgO more than 9.5 and be less than 13, CaO 4～9, SrO 0.5～4.5, BaO 0～1, ZrO20～2, MgO+CaO+SrO+BaO are 17～21, and MgO/ (MgO+CaO+SrO+BaO) is more than 0.40, and MgO/ (MgO+CaO) is more than 0.40, and MgO/ (MgO+SrO) is more than 0.60.
Description
Technical field
The present invention relates to be suitable as various glass substrate for display, photomask glass substrate, by using hydrogen fluorine
The etch processes of acid (HF) has carried out alkali-free glass substrate that is thinning and that contain substantially no alkali metal oxide and alkali-free glass
The thining method of glass substrate.
Background technology
In the past, for various glass substrate for display, the most from the teeth outwards formation metal or sull etc.
Glass substrate, it is desirable to characteristic shown below.
(1) time containing alkali metal oxide, alkali metal ion can spread in thin film and make membrane property deteriorate, and therefore,
Contain substantially no alkali metal ion.
(2) when being exposed to high temperature in thin film formation process, in order to by the deformation of glass with the Stability Analysis of Structures of glass
Change contraction (thermal contraction) suppression produced and want height at bottom line, strain point.
(3) the various chemicals that quasiconductor is formed middle use to have sufficient chemical durability.Particularly to being used for
SiOx、SiNxThe buffered hydrofluoric acid (BHF, the mixed liquor of Fluohydric acid. and ammonium fluoride) of etching and the etching of ITO in use contain
The various acid (nitric acid, sulphuric acid etc.) used in the etching of the medicinal liquid of hydrochloric acid, metal electrode, the alkali of anticorrosive additive stripping liquid controlling is had to have
Durability.
(4) inside and surface are without defect (bubble, brush line, field trash, pit, scar etc.).
On the basis of above-mentioned requirements, have also appeared situation as described below in recent years.
(5) lightweight of display is required, it is desirable to glass itself is also the glass that density is little.
(6) lightweight of display is required, it is desirable to thinning glass substrate.
(7) in addition to non-crystalline silicon (a-Si) type liquid crystal display up to now, heat treatment temperature has also been made slightly higher
Polysilicon (p-Si) type liquid crystal display (a-Si: about 350 DEG C → p-Si:350～550 DEG C).
(8) productivity ratio or raising are improved in order to accelerate to make the liter gentleness cooling rate of the heat treatment of liquid crystal display
Resistance to sudden heating, it is desirable to the glass that the mean thermal expansion coefficients of glass is little.
On the other hand, dry etching is developed, and the requirement to resistance to BHF weakens.In order to make resistance to BHF good, so far
Till the many uses of glass contain the B of 6～10 moles of %2O3Glass.But, B2O3There is the tendency making strain point reduce.Make
For without B2O3Or B2O3The example of poor alkali-free glass, has glass as described below.
Patent Document 1 discloses and do not contain B2O3SiO2-Al2O3-SrO glass, but the temperature needed for fusing is high, in system
Make middle generation difficulty.
Patent Document 2 discloses and do not contain B2O3SiO2-Al2O3-SrO glass ceramics, but the temperature needed for fusing is high,
Produce difficulty in the mill.
Patent Document 3 discloses the B containing 0～3 weight %2O3Glass, but the strain point of embodiment be 690 DEG C with
Under.
Patent Document 4 discloses the B containing 0～5 mole of %2O3Glass, but evenly heat at 50～300 DEG C expands
Coefficient is more than 50 × 10-7/℃。
Patent Document 5 discloses the B containing 0～5 mole of %2O3Glass, but thermal expansion is big, and density is the biggest.
For the problem solving the glass described in patent documentation 1～5, it is proposed that the alkali-free glass described in patent documentation 6
Glass.The strain point of the alkali-free glass described in patent documentation 6 is high, it is possible to by float forming, be suitable for base plate for displaying, light
The purposes such as mask substrate.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 62-113735 publication
Patent documentation 2: Japanese Laid-Open Patent Publication 62-100450 publication
Patent documentation 3: Japanese Unexamined Patent Publication 4-325435 publication
Patent documentation 4: Japanese Unexamined Patent Publication 5-232458 publication
Patent documentation 5: No. 5326730 description of U.S. Patent No.
Patent documentation 6: Japanese Unexamined Patent Publication 10-45422 publication
Patent documentation 7: Japan's public table patent 2009-066624 publication again
Summary of the invention
Invent problem to be solved
On the other hand, middle-size and small-size liquid crystal display (LCD), organic el display (OELD), particularly mobile phone,
In the field of the portable display such as digital camera, mobile phone, the lightweight of display, slimming have become important problem.
In order to realize the thinning of glass substrate further, widely used following operation: after array light filter bonding process, to glass base
Etch processes is implemented on plate surface, makes thickness of slab thinning (thinning).Such as, following operation is carried out: utilize the erosion containing Fluohydric acid. (HF)
Carve liquid to be etched the surface of the glass substrate that thickness of slab is 0.4mm～0.7mm processing (hereinafter referred to as " at hydrofluoric acid etch
Reason "), make the glass substrate (with reference to patent documentation 7) that thickness of slab is 0.1mm～0.4mm.
In the case of being processed thinning glass substrate by hydrofluoric acid etch, it is desirable to: when (1) hydrofluoric acid etch processes
Etching speed wants big；And the glass substrate after (2) etch processes to have sufficient intensity.
But, although there is the solid-phase crystallization method manufacture method as the p-Si TFT of high-quality, but in order to implement the method,
Require to improve strain point further.
On the other hand, based on technology for making glass, particularly melt, shape in requirement, need reduce glass viscosity,
Particularly glass viscosity reaches 104Temperature T during dPa s4。
It is an object of the invention to solve disadvantages mentioned above, it is provided that strain point is high, viscosity is low, particularly glass viscosity reaches
104Temperature T during dPa s4Etching speed when low, hydrofluoric acid etch processes is big, hydrofluoric acid etch process after intensity high,
Even if making thin be not easy to bending and apply stress and be not easy to produce alkali-free glass substrate and the alkali-free glass of the problem such as irregular colour
The thining method of glass substrate.
Means for solving the above
The present invention provides a kind of alkali-free glass substrate (1), and it is for be thinned more than 5 μm by Fluohydric acid. (HF) etch processes
, thickness of slab be the alkali-free glass substrate of below 0.4mm, described alkali-free glass substrate is following alkali-free glass, thinning after described
The specific modulus of alkali-free glass substrate is more than 32MNm/kg, and photoelastic constant is below 31nm/MPa/cm,
The strain point of described alkali-free glass is more than 710 DEG C, and glass viscosity reaches 102Temperature T during dPa s2It is 1710
Below DEG C, glass viscosity reaches 104Temperature T during dPa s4It is less than 1320 DEG C, contains in terms of based on oxide mole of %:
MgO+CaO+SrO+BaO is 17～21,
MgO/ (MgO+CaO+SrO+BaO) is more than 0.40,
MgO/ (MgO+CaO) is more than 0.40,
MgO/ (MgO+SrO) is more than 0.60.
It addition, the present invention provides a kind of alkali-free glass substrate (2), it is for be thinned 5 μ by Fluohydric acid. (HF) etch processes
More than m, thickness of slab be the alkali-free glass substrate of below 0.4mm, described alkali-free glass substrate is following alkali-free glass, thinning after
The specific modulus of described alkali-free glass substrate is more than 32MNm/kg, and photoelastic constant is below 31nm/MPa/cm,
The strain point of described alkali-free glass is more than 710 DEG C, and glass viscosity reaches 102Temperature T during dPa s2It is 1710
Below DEG C, glass viscosity reaches 104Temperature T during dPa s4It is less than 1320 DEG C, contains in terms of based on oxide mole of %:
MgO+CaO+SrO+BaO is more than 18.2 and is less than 21,
MgO/ (MgO+CaO+SrO+BaO) is more than 0.25,
MgO/ (MgO+CaO) is more than 0.3,
MgO/ (MgO+SrO) is more than 0.60,
Al2O3× (MgO/ (MgO+CaO+SrO+BaO)) is more than 5.5.
The alkali-free glass substrate (1) of the present invention, mean thermal expansion coefficients at 50～350 DEG C of (2) are preferably 30 × 10-7
～43 × 10-7/℃。
The alkali-free glass substrate (1) of the present invention, (2) are preferably by the ring and the diameter that use a diameter of 30mm, R to be 2.5mm
The mean fracture load measured for ball (BOR) method of the ball of 10mm is scaled more than 300N with the thickness of slab of 0.4mm.
It addition, the present invention provides the thining method (1) of a kind of alkali-free glass substrate, it is the thinning side of alkali-free glass substrate
Method, wherein,
Described alkali-free glass substrate is following alkali-free glass, is being impregnated by least one interarea of described alkali-free glass substrate
Unit are and the stripping quantity of unit interval time in the etching solution (25 DEG C, 5%HF aqueous solution) containing Fluohydric acid. (HF) reach
To 0.17 (mg/cm2)/minute more than under conditions of, more than thinning for described alkali-free glass substrate 5 μm,
The strain point of described alkali-free glass is more than 710 DEG C, and glass viscosity reaches 102Temperature T during dPa s2It is 1710
Below DEG C, glass viscosity reaches 104Temperature T during dPa s4It is less than 1320 DEG C, contains in terms of based on oxide mole of %:
MgO+CaO+SrO+BaO is 17～21,
MgO/ (MgO+CaO+SrO+BaO) is more than 0.40,
MgO/ (MgO+CaO) is more than 0.40,
MgO/ (MgO+SrO) is more than 0.60.
It addition, the present invention provides the thining method (2) of a kind of alkali-free glass substrate, it is the thinning side of alkali-free glass substrate
Method, wherein,
Described alkali-free glass substrate is following alkali-free glass, is being impregnated by least one interarea of described alkali-free glass substrate
Unit are and the stripping quantity of unit interval time in the etching solution (25 DEG C, 5%HF aqueous solution) containing Fluohydric acid. (HF) reach
To 0.17 (mg/cm2)/minute more than under conditions of, more than thinning for described alkali-free glass substrate 5 μm,
The strain point of described alkali-free glass is more than 710 DEG C, and glass viscosity reaches 102Temperature T during dPa s2It is 1710
Below DEG C, glass viscosity reaches 104Temperature T during dPa s4It is less than 1320 DEG C, contains in terms of based on oxide mole of %:
MgO+CaO+SrO+BaO is more than 18.2 and is less than 21,
MgO/ (MgO+CaO+SrO+BaO) is more than 0.25,
MgO/ (MgO+CaO) is more than 0.3,
MgO/ (MgO+SrO) is more than 0.60,
Al2O3× (MgO/ (MgO+CaO+SrO+BaO)) is more than 5.5.
Invention effect
The strain point of the alkali-free glass substrate of the present invention is high, and glass viscosity reaches 104Temperature T during dPa s4Low, hydrogen fluorine
Etching speed when acid etching processes is big, and the intensity after hydrofluoric acid etch processes is high, is not easy to bending, even and if executing even if thin
Add stress and be not easy to produce the problems such as irregular colour, therefore, be suitable as at middle-size and small-size LCD, OLED, particularly mobile electricity
The thin glass substrate that thickness of slab is below 0.4mm used in the field of the portable displays such as words, digital camera, mobile phone.This
The alkali-free glass substrate of invention can also use as glass substrate for disc.
Detailed description of the invention
Hereinafter, the thining method of the alkali-free glass substrate of the present invention is illustrated.
In the thining method (1) of the alkali-free glass substrate of the present invention, use and utilize in the way of reaching following glass composition 1
The alkali-free glass substrate of the frit of allotment.
This alkali-free glass contains in terms of based on oxide mole of %:
MgO+CaO+SrO+BaO is 17～21,
MgO/ (MgO+CaO+SrO+BaO) is more than 0.40,
MgO/ (MgO+CaO) is more than 0.40,
MgO/ (MgO+SrO) is more than 0.60.
It addition, in the thining method of the alkali-free glass substrate of the present invention (2), use and utilize to reach following glass composition 2
The alkali-free glass substrate of frit allocated of mode.
This alkali-free glass contains in terms of based on oxide mole of %:
MgO+CaO+SrO+BaO is more than 18.2 and is less than 21,
MgO/ (MgO+CaO+SrO+BaO) is more than 0.25,
MgO/ (MgO+CaO) is more than 0.3,
MgO/ (MgO+SrO) is more than 0.60,
Al2O3× (MgO/ (MgO+CaO+SrO+BaO)) is more than 5.5.
Then, the compositing range of each composition is illustrated.SiO2Less than 66% (mole %, the most unless otherwise noted
The most identical) time, strain point cannot fully improve, and thermal coefficient of expansion increases, and density rises.Preferably more than 66.5%, more
It is preferably more than 67%.During more than 70%, etching speed reduces, and the melting of glass reduces, and devitrification temperature rises.It is preferably
Less than 69%.
Al2O3Improve Young's modulus, suppress thinning after bending, and suppress the split-phase of glass, reduce thermal expansion system
Number, improves strain point, and Fracture Toughness improves, and improves strength of glass, but during less than 12%, does not show this effect, it addition, can make
Other increase the composition expanded and increase, and result thermal expansion increases.It is preferably more than 12.2%.During more than 15%, glass may be made
The melting of glass is deteriorated or makes devitrification temperature increase.Preferably less than 14.5%, more preferably less than 14%, further preferably
It is less than 13.8%.
B2O3The fusing improving glass is reactive, and reduces devitrification temperature, therefore, it can add to 1.5%.But too much
Time, photoelastic constant increases, and easily produces the problems such as irregular colour when applying stress.It addition, B2O3Time too much, thinning after
Surface roughness increase, thinning after intensity reduce.Additionally, strain point also reduces.It is therefore preferable that be less than 1.3%, more preferably
It is less than 1%, preferably contains substantially no.
MgO does not improves proportion and improves Young's modulus, therefore, by improving specific modulus, it is possible to the problem alleviating bending.Separately
Outward, have in alkaline-earth metal and do not increase the feature expanding and not making strain point excessively reduce, also improve melting.It addition, it is disconnected
Split toughness value to improve, improve strength of glass.
Herein, in glass composition 1, content of MgO is more than 9.5% and is less than 13%.Time below 9.5%, above-mentioned by
MgO adds the effect brought and cannot fully show.But, when more than 13%, devitrification temperature likely rises.It is preferably
Less than 12.5%, more preferably less than 12%, more preferably less than 11.5%.
On the other hand, in glass composition 2, content of MgO is 5～9.5%.During less than 5%, above-mentioned being added by MgO brings
Effect cannot fully show.It is preferably more than 6%, more preferably more than 7%.But, during more than 9.5%, devitrification temperature has
May rise.It is preferably less than 9.3%, more preferably less than 9%.
In alkaline-earth metal, CaO is only second to MgO and has raising specific modulus, do not increase expansion and do not make strain point excessively drop
Low feature, also improves melting.
Herein, in glass composition 1, CaO content is 4～9%.During less than 4%, above-mentioned is added, by CaO, the effect brought
Cannot fully show.But, during more than 9%, devitrification temperature may be made to raise or make the limestone as CaO raw material
(CaCO3Foreign matter of phosphor in) is mixed in a large number.It is preferably less than 7%, more preferably less than 6%, more preferably less than 5%.
On the other hand, in glass composition 2, CaO content is 4～11%.During less than 4%, above-mentioned added by CaO brings
Effect cannot fully show.It is preferably more than 5%.But, during more than 11%, devitrification temperature may be made to raise or make conduct
Limestone (the CaCO of CaO raw material3Foreign matter of phosphor in) is mixed in a large number.It is preferably less than 10%, more preferably less than 9%, enters one
Step is preferably less than 7%, particularly preferably less than 6%.
SrO raising melting is without making the devitrification temperature of glass raise, but during less than 0.5%, this effect can not be abundant
Performance.It is preferably more than 1.0%, more preferably more than 2.0%.But, during more than 4.5%, the coefficient of expansion may increase
Greatly.More preferably less than 4.0%, more preferably less than 3.5%.
BaO is optional, but can contain to improve melting.But, time too much, can make glass expansion and
Density excessively increases, and is therefore set as less than 1%.Preferably shorter than 1%, more preferably less than 0.5%, the most substantially
Do not contain.
In order to improve Young's modulus, reduce glass melting temperature or in order to promote crystallization during calcining, Ke Yihan
There is the ZrO of less than 2%2.During more than 2%, glass becomes unstable or glass relative dielectric constant ε and increases.It is preferably
Less than 1.5%, more preferably less than 1.0%, more preferably less than 0.5%, particularly preferably contain substantially no.
Glass composition 1 in, if MgO, CaO, SrO, BaO in terms of total amount less than 17%, then etching speed is slack-off, photoelasticity is normal
Number becomes big, and melting reduces.It is preferably more than 18%, more preferably more than 18.5%.If more than 21%, then may
The difficulty that cannot reduce thermal coefficient of expansion can be produced.It is preferably less than 20%.
In glass composition 2, if MgO, CaO, SrO, BaO are calculated as less than 18.2% with total amount, then etching speed is slack-off, photoelastic
Property constant become big, and melting reduces.If more than 21%, then the difficulty that cannot reduce thermal coefficient of expansion may be produced.Excellent
Elect less than 20% as.
In glass composition 1, meet above-mentioned condition by the total amount making MgO, CaO, SrO and BaO and meet following three bar
Part, specific modulus is high, it is possible to improve strain point in the case of not making devitrification temperature increase, and can reduce glass viscosity,
Particularly glass viscosity reaches 104Temperature T during dPa s4.It addition, Fracture Toughness improves, it is possible to increase strength of glass.
MgO/ (MgO+CaO+SrO+BaO) is more than 0.4, preferably more than 0.45.
MgO/ (MgO+CaO) is more than 0.4, preferably more than 0.52, more preferably more than 0.55.
MgO/ (MgO+SrO) is more than 0.6, preferably more than 0.7.
In glass composition 2, meet above-mentioned condition by the total amount making MgO, CaO, SrO and BaO and meet following three bar
Part, specific modulus is high, it is possible to improve strain point in the case of not making devitrification temperature increase, and can reduce glass viscosity,
Particularly glass viscosity reaches 104Temperature T during dPa s4.It addition, Fracture Toughness improves, it is possible to increase strength of glass.
MgO/ (MgO+CaO+SrO+BaO) is more than 0.25, preferably more than 0.3, more preferably more than 0.4, further
It is preferably more than 0.45.
MgO/ (MgO+CaO) is more than 0.3, preferably more than 0.4, more preferably more than 0.52, more preferably
More than 0.55.
MgO/ (MgO+SrO) is more than 0.6, preferably more than 0.7.
In glass composition 2, Al2O3When × (MgO/ (MgO+CaO+SrO+BaO)) is more than 5.5, it is possible to increase Young mould
Amount, the most preferably.It is preferably more than 5.75, more preferably more than 6.0, more preferably more than 6.25, particularly preferably 6.5
Above.
Na can be added for purposes such as electricity auxiliary heating2O、K2The alkali metal oxides such as O.If alkali metal oxide
Content improves, then alkali metal ion can spread in the film and make membrane property deteriorate, therefore, as various base plate for displaying
Glass becomes problem when using, if but to make the content of alkali metal oxide in glass composition be below 2000 molar ppm, the most not
It is easily generated such problem.Below more preferably 1500 molar ppm, below 1300 molar ppm, below 1000 molar ppm.
It addition, in order to not make to be located at the gold of glass surface when the alkali-free glass substrate of the use present invention is to manufacture display
Belong to or sull produces deterioration in characteristics, preferably frit and contains substantially no P2O5.Additionally, in order to make glass the most again
Utilizing, preferably frit contains substantially no PbO, As2O3、Sb2O3。
In order to improve the melting of glass, clarification, formability, can add total amount in frit is less than 5%
ZnO, Fe2O3、SO3、F、Cl、SnO2。
The manufacture of the alkali-free glass substrate of the present invention is such as implemented according to following steps.
The raw material of each composition is allocated in the way of reaching target component (above-mentioned glass composition 1,2), it is continuous
Put in fusing stove, be heated to 1500～1800 DEG C and make it melt.This melten glass forming device is configured to predetermined thickness of slab
The glass tape of tabular, cut after this glass tape is annealed, it is possible to obtain alkali-free glass substrate.
In the present invention, it is the glass tape of tabular preferably by float forming.
In the thining method of the alkali-free glass substrate of the present invention, by two interareas to alkali-free glass substrate at least
One interarea carries out Fluohydric acid. (HF) etch processes, more than thinning for this alkali-free glass substrate 5 μm.By thinning, it is possible to reduce
Use the thickness of the display of alkali-free glass substrate, and display lightweight can be made.
If the process of obstructed overetch carries out thinning but just uses, from initially, the alkali-free glass substrate that thin plate, i.e. thickness of slab are little,
The element manufacturing operation then implemented when display manufacturing etc. need to process big thin plate, thus easily produces deadweight
Carrying obstacle (the generation etc. of the scar on substrate that such as, contact during carrying is caused caused by bending.The most identical), base
The problem such as rupture of plate.More than the most thinning 10 μm, more than the most thinning 100 μm, the most thinning 200 μm with
On.
In the thining method of the alkali-free glass substrate of the present invention, thinning after the thickness of slab of alkali-free glass substrate be 0.4mm with
Under.During more than 0.4mm, it is impossible to obtain the effect of the lightweight of display, slimming.More preferably below 0.35mm, further
It is preferably below 0.25mm.
The thickness of slab carrying out thinning front alkali-free glass substrate is preferably more than 0.3mm.If less than 0.3mm, then in device system
Make operation etc. needs to process big thin plate, thus easily produce the carrying obstacle caused by deadweight bending, rupture etc. and to ask
Topic.More preferably more than 0.4mm, particularly preferably more than 0.45mm.But, if more than 0.75mm, then it is used for the light of display
Quantify, the thinning required time of slimming likely becomes long.More preferably below 0.65mm, more preferably
Below 0.55mm.
Medicinal liquid for etch processes uses the medicinal liquid comprising Fluohydric acid. (HF).The medicinal liquid that can also utilize alkalescence loses
Quarter processes, but comprises the etching speed of the medicinal liquid of Fluohydric acid. faster, and can etch more smooth.The hydrogen fluorine comprised in medicinal liquid
Acid concentration is more preferably more than 1 mass %, more preferably more than 3 mass %, more than particularly preferably 5 mass %.It addition,
In addition to Fluohydric acid., in medicinal liquid, preferably add the acid beyond the Fluohydric acid .s such as hydrochloric acid, nitric acid, sulphuric acid.
During etch processes, at least one interarea of alkali-free glass substrate is impregnated in the medicinal liquid comprising Fluohydric acid..According to
The Funing tablet dipping scheduled time in medicinal liquid, thus by thinning for alkali-free glass substrate scheduled volume.
In etch processes, preferably made by least any one the above method in stirring, bubbling, ultrasound wave, spray
Liquid medicine flow.At least any one the above method in shake, rotation can also be utilized to make alkali-free glass substrate move generation
For making liquid medicine flow.
In the thining method of the alkali-free glass substrate of the present invention, time in the 5 mass % Fluohydric acid .s (HF) that impregnated in 25 DEG C,
The index as etching speed, unit are and the stripping quantity of unit interval reach 0.17 (mg/cm2)/minute more than
Under the conditions of implement etch processes.If less than 0.17 (mg/cm2)/minute, the most thinning required time likely becomes long.
More preferably 0.18 (mg/cm2)/minute more than.
By in the alkali-free glass substrate that the method for the present invention is thinning, thinning after intensity high.Specifically, by using
A diameter of 30mm, R are the ball of the ball of the ring (cross section of ring for circle, R is the radius of this circle) of 2.5mm and a diameter of 10mm
(BOR) method (making the table wanting the side being evaluated be placed face down on ring) to the alkali-free glass substrate after thinning through erosion
The mean fracture load that the interarea (wanting the surface of the side being evaluated) of the side that quarter processes is measured is with the plate of 0.4mm
Thick conversion is preferably more than 300N.Herein, the diameter of ring refers to the diameter of a circle by cross section central authorities, at diameter 30mm, R=
In the case of the ring of 2.5mm, the external diameter of ring is 35mm, innermost diameter is 25mm.
It addition, mean fracture load refers to, the mensuration of breaking load based on BOR method is implemented repeatedly thus obtained
The meansigma methods of measurement result.It addition, in embodiment described later, implement the mensuration of 5 breaking loads based on BOR method, by it
The meansigma methods of measurement result as mean fracture load.
If the mean fracture load measured by BOR method is converted less than 300N, then alkali-free glass substrate with the thickness of slab of 0.4mm
Surface strength low, glass substrate ruptures etc. and (such as, to mention with supporting pin etc. during process when display manufacturing etc.
In the operation of the alkali-free glass substrate after element manufacturing etc, glass substrate ruptures), thinning after intensity may become
For problem.More preferably more than 350N.
The thickness of slab conversion utilizing BOR method is carried out according to below step.
In BOR method, square being inversely proportional to, therefore, by glass substrate of stress and the thickness of slab produced at glass baseplate surface
Thickness of slab be set to t (mm), time the breaking load obtained by BOR method is set to w (N), carry with the fracture that the thickness of slab of 0.4mm converts
Lotus W (N) can pass through W=w × 0.16/t2Relational expression obtain.
By in the method for present invention alkali-free glass substrate after thinning, thinning after alkali-free glass substrate through overetch
The surface strength based on three-point bending of the interarea (wanting the surface of the side being evaluated) of the side processed is preferably
More than 500MPa.If less than 500MPa, then use thinning after the display of alkali-free glass substrate as portable display
During use, it is possible to easily produce problems such as rupturing.More preferably more than 800MPa, more preferably more than 1000MPa, special
You Xuanwei more than 1200MPa, most preferably more than 1500MPa.
The interarea of the side through etch processes of the alkali-free glass substrate after thinning (wants the table of the side being evaluated
Face) surface strength based on three-point bending measure as follows.When evaluation face is protected with paster, draw with point scriber
Glass substrate, after cutting, the paster in evaluation face of tearing, with uncrossed side under mode be arranged at span as 10mm, R be
On the three-point bending fixture of 1.5mm.Extruding from line side above with the fixture that R is 1.5mm, breaking load time thus calculates
Go out surface strength based on three-point bending.
If there being scar on evaluation face, then intensity reduces, and therefore, needs to tie up when not contacting evaluation face after thinning
Hold.In bend test, in the case of end face exists break origins, mensuration is end face strength rather than surface strength, thus
It is positioned at result of the test during face only with starting point, obtains mean fracture load.
It addition, in this specification, environment set when by BOR method or measuring mean fracture load by three-point bending is
Temperature 22 ± 2 DEG C, humidity 40 ± 10%.
For the alkali-free glass substrate that the method by the present invention is thinning, thinning after the process of alkali-free glass substrate
The surface roughness of the interarea of the side of the etch processes Ra that 1 μm is square in AFM measures is preferably below 0.75nm.If being more than
0.75nm, then the intensity of alkali-free glass substrate is likely to decrease.More preferably below 0.7nm.
In the present invention, the strain point of the alkali-free glass substrate of above-mentioned glass composition 1,2 is more than 710 DEG C, it is possible to suppression makes
With the thermal contraction during display manufacturing of this alkali-free glass substrate.It addition, solid-phase crystallization method can be applied as showing at LCD etc.
The manufacture method of the p-Si TFT implemented in device manufacturing process.More preferably more than 715 DEG C, more preferably more than 720 DEG C.
Particularly preferably more than 735 DEG C.If strain point is more than 735 DEG C, then (such as, OLED's is aobvious to be suitable for high strain-point purposes
Show device substrate or illumination substrate or thin base plate for displaying that thickness of slab is below 100 μm or illumination substrate).
But, if the strain point of glass is too high, then need to improve correspondingly the temperature of forming device, forming device
Life-span declines.Therefore, the strain point of the plate glass of the present invention is less than 750 DEG C.
It addition, order the same reason, the glass transition of the alkali-free glass substrate of above-mentioned glass composition 1,2 based on strain
Temperature is preferably more than 760 DEG C, more preferably more than 770 DEG C, more preferably more than 780 DEG C.
It addition, the evenly heat that the alkali-free glass substrate of above-mentioned glass composition 1,2 is at 50～300 DEG C, preferably 50～350 DEG C
The coefficient of expansion is preferably 30 × 10-7～43 × 10-7/ DEG C, resistance to sudden heating is big, it is possible to increase use this alkali-free glass substrate
Productivity ratio during display manufacturing.In the glass of the present invention, the evenly heat at 50～300 DEG C, preferably 50～350 DEG C expands system
Number more preferably 35 × 10-7～40 × 10-7/℃。
Additionally, the proportion of alkali-free glass substrate of above-mentioned glass composition 1,2 is preferably less than 2.65, more preferably 2.64 with
Under, more preferably less than 2.62.
It addition, the specific modulus of the alkali-free glass substrate of above-mentioned glass composition 1,2 is more than 32MNm/kg.If less than 32MNm/
Kg, then easily produce carrying obstacle, the problem such as rupture because deadweight bending.More preferably more than 33MNm/kg.
It addition, the Young's modulus of the alkali-free glass substrate of above-mentioned glass composition 1,2 is preferably more than 84GPa, the most excellent
Elect more than 86GPa as, more preferably more than 88GPa, more preferably more than 90GPa.
It addition, the photoelastic constant of the alkali-free glass substrate of above-mentioned glass composition 1,2 is below 31nm/MPa/cm.
It is double that the stress produced in LCD manufacturing process or when LCD device uses makes the glass substrate used in display have
Refrangibility, thus, observes the phenomenon that black display contrast graying, liquid crystal display reduces sometimes.Photoelastic by making
Property constant be below 31nm/MPa/cm, it is possible to by this phenomenon suppress in relatively low limit.It is preferably below 30nm/MPa/cm, more excellent
Elect below 29nm/MPa/cm as, more preferably below 28.5nm/MPa/cm, particularly preferably below 28nm/MPa/cm.
If it is considered that guarantee the easness of other physical property, then photoelastic constant is preferably more than 23nm/MPa/cm, more preferably
For more than 25nm/MPa/cm.
It addition, photoelastic constant can be measured under measuring wavelength 546nm by disk compression method.
It addition, the relative dielectric constant of the alkali-free glass substrate of above-mentioned glass composition 1,2 is preferably more than 5.6.
At embedded touch control panel such described in Japanese Unexamined Patent Publication 2011-70092 publication (in display panels
It is built-in with the contact panel of touch sensing) in the case of, from improving the induction sensitivity of touch sensing, reducing driving electricity
From the viewpoint of pressure, saving electric power, the relative dielectric constant of glass substrate is the highest more good.By making relative dielectric constant be 5.6
Above, the induction sensitivity of touch sensing improves.It is preferably more than 5.8, more preferably more than 6.0, more preferably 6.2
Above, particularly preferably more than 6.4.
It addition, relative dielectric constant can be measured by the method described in JIS C-2141.
It addition, the viscosities il of the alkali-free glass substrate of above-mentioned glass composition 1,2 reaches 102Temperature T during pool (dPa s)2For
Less than 1710 DEG C, preferably shorter than 1710 DEG C, more preferably less than 1700 DEG C, more preferably less than 1690 DEG C, thus compare
Easily fusing.
Additionally, the viscosities il of the alkali-free glass substrate of above-mentioned glass composition 1,2 reaches 104Temperature T during pool4Be 1320 DEG C with
Under, preferably less than 1315 DEG C, more preferably less than 1310 DEG C, more preferably less than 1305 DEG C, it is suitable for float forming.
It addition, from the viewpoint of easily by float forming, the alkali-free glass substrate of the most above-mentioned glass composition 1,2
Devitrification temperature is less than 1350 DEG C.It is preferably less than 1340 DEG C, more preferably less than 1330 DEG C.
Devitrification temperature in this specification obtains as follows: the glass particle after pulverizing is put in the ware of platinum, is controlling
In the electric furnace of uniform temperature, carry out the heat treatment of 17 hours, obtained at glass by the observation by light microscope after heat treatment
Surface and the internal minimum temperature separating out the maximum temperature crystallized and not separating out crystallization, be averaged value as devitrification temperature.
Embodiment
(embodiment 1,2, comparative example 1)
The raw material of each composition is allocated in the way of reaching the composition of the target shown in table 1, utilizes continuous melting furnaces to carry out
Fusing, carries out plate forming by float glass process, obtains alkali-free glass substrate.
After obtained glass substrate is carried out mirror ultrafinish, by utilizing 8 mass % Fluohydric acid .s, 10 mass % hydrochloric acid
Mixed acid carries out the etch processes of the one side of glass substrate while carrying out bubbling so that thickness of slab becomes 0.4mm from 0.7mm,
Thus carry out thinning.
Use thinning after glass substrate, by using the SUS ring of a diameter of 30mm, R=2.5mm and a diameter of 10mm
Ball (BOR) method of SUS ball implement the mensuration of 5 breaking loads, by obtained by these measurement results with the plate of 0.4mm
The mean fracture load of thick conversion is shown in Table 2.
It addition, in the case of by step similar to the above by thickness of slab etch processes 30 μm, asked by following method
Go out the surface roughness in etch processes face.Show the result in table 2 below.
[assay method of surface roughness based on AFM]
For the etch processes face of glass substrate, utilize the XE-HDM that Park Systems company manufactures, by sweep speed
It is set as 1Hz, obtains the surface roughness Ra that 1 μm is square.
Additionally, the index of etching speed when processing as hydrofluoric acid etch, as steps described below to by alkali-free glass base
Plate is impregnated into 25 DEG C, in the hydrofluoric acid aqueous solution of 5 mass % time unit are and the stripping quantity of unit interval evaluated.
Show the result in table 2.
[assay method of the stripping quantity of unit are and unit interval]
To being cut into after alkali-free glass substrate square for 40mm is carried out through mirror ultrafinish, quality measurement.At 25 DEG C
5 mass % Fluohydric acid .s in impregnate 20 minutes, measure dipping after quality.Calculated surface area by sample size, quality is subtracted
After on a small quantity divided by surface area, then divided by dip time, thus obtain the stripping quantity of unit are and unit interval.
It addition, about the alkali-free glass substrate obtained by above-mentioned steps, also measured were strain point, Young's modulus, compare mould
Amount, photoelastic constant.Show the result in table 2.
[table 1]
[table 2]
(embodiment 3～5, comparative example 2)
The raw material of each composition is allocated in the way of reaching the composition of the target shown in the embodiment 3～5 of table 3, uses
Platinum crucible melts 1 hour at a temperature of 1650 DEG C.After fusing, flow out into carbon plate shape, in the temperature of glass transition temperature+30 DEG C
After the lower holding of degree 1 hour, cool down with 1 DEG C/min, anneal, obtain alkali-free glass substrate.
After obtained glass substrate is carried out mirror ultrafinish, by utilizing 8 mass % Fluohydric acid .s, 10 mass % hydrochloric acid
Mixed acid carries out the etch processes of the one side of glass substrate while carrying out bubbling so that thickness of slab becomes 0.4mm from 0.7mm,
Thus carry out thinning.
Use thinning after glass substrate, by using the SUS ring of a diameter of 30mm, R=2.5mm and a diameter of 10mm
Ball (BOR) method of SUS ball implement the mensuration of 5 breaking loads, by obtained by these measurement results with the plate of 0.4mm
The mean fracture load of thick conversion is shown in Table 4.
It addition, in the case of by step similar to the above by thickness of slab etch processes 30 μm, asked by said method
Go out the surface roughness in etch processes face.Show the result in table 4.
Alkali-free glass substrate is impregnated into 25 DEG C, in the hydrofluoric acid aqueous solution of 5 mass % additionally, obtained by said method
Time unit are and the stripping quantity of unit interval.Show the result in table 4.
It addition, about the alkali-free glass substrate obtained by above-mentioned steps, also measured were strain point, Young's modulus, compare mould
Amount, photoelastic constant.Show the result in table 4.It addition, in table 3～4, be value of calculation by the value shown in bracket.
[table 3]
| Mole % | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 2 |
| SiO2 | 67.1 | 67.1 | 67.2 | 70 |
| Al2O3 | 13.5 | 13.6 | 13.8 | 13 |
| B2O3 | 0.0 | 0.7 | 0.4 | 1 |
| MgO | 9.8 | 10.1 | 7.5 | 5 |
| CaO | 5.3 | 4.1 | 8.6 | 5 |
| SrO | 4.3 | 4.4 | 2.5 | 2 |
| BaO | 0 | 0 | 0 | 4 |
| ZrO2 | 0 | 0 | 0 | 0 |
| MgO+CaO+SrO+BaO | 19.4 | 18.6 | 18.5 | 16 |
| MgO/(MgO+CaO+SrO+BaO) | 0.51 | 0.54 | 0.40 | 0.31 |
| MgO/(MgO+CaO) | 0.65 | 0.71 | 0.47 | 0.5 |
| MgO/(MgO+SrO) | 0.70 | 0.70 | 0.75 | 0.71 |
| Al2O3×(MgO/(MgO+CaO+SrO+BaO)) | 6.8 | 7.4 | 5.6 | 4.1 |
[table 4]
With reference to specific embodiment, the present invention is described in detail, but without departing from the spirit and scope of the present invention
In the case of can make various changes and modifications, this is apparent to those skilled in the art.
The Japanese patent application 2012-124760 that the application proposed based on May 31st, 2012, by its content with reference
Form is incorporated in this specification.
Claims (7)
1. an alkali-free glass substrate, its for by Fluohydric acid. (HF) etch processes be thinned more than 5 μm, thickness of slab be 0.4mm
Following alkali-free glass substrate, described alkali-free glass substrate is following alkali-free glass, thinning after described alkali-free glass substrate
Specific modulus is more than 32MNm/kg, and photoelastic constant is below 31nm/MPa/cm,
The strain point of described alkali-free glass is more than 710 DEG C, and glass viscosity reaches 102Temperature T during dPa s2Be 1710 DEG C with
Under, glass viscosity reaches 104Temperature T during dPa s4It is less than 1320 DEG C, contains in terms of based on oxide mole of %:
MgO+CaO+SrO+BaO is 17～21,
MgO/ (MgO+CaO+SrO+BaO) is more than 0.40,
MgO/ (MgO+CaO) is more than 0.40,
MgO/ (MgO+SrO) is more than 0.60.
2. an alkali-free glass substrate, its for by Fluohydric acid. (HF) etch processes be thinned more than 5 μm, thickness of slab be 0.4mm
Following alkali-free glass substrate, described alkali-free glass substrate is following alkali-free glass, thinning after described alkali-free glass substrate
Specific modulus is more than 32MNm/kg, and photoelastic constant is below 31nm/MPa/cm,
The strain point of described alkali-free glass is more than 710 DEG C, and glass viscosity reaches 102Temperature T during dPa s2Be 1710 DEG C with
Under, glass viscosity reaches 104Temperature T during dPa s4It is less than 1320 DEG C, contains in terms of based on oxide mole of %:
MgO+CaO+SrO+BaO is more than 18.2 and is less than 21,
MgO/ (MgO+CaO+SrO+BaO) is more than 0.25,
MgO/ (MgO+CaO) is more than 0.3,
MgO/ (MgO+SrO) is more than 0.60,
Al2O3× (MgO/ (MgO+CaO+SrO+BaO)) is more than 5.5.
3. alkali-free glass substrate as claimed in claim 1 or 2, wherein, the mean thermal expansion coefficients at 50～350 DEG C is 30 ×
10-7～43 × 10-7/℃。
4. alkali-free glass substrate as claimed in claim 1 or 2, wherein, described alkali-free glass substrate is a diameter of by using
30mm, R are the mean fracture load that measures of ball (BOR) method of the ball of the ring of 2.5mm and a diameter of 10mm thickness of slab with 0.4mm
It is scaled more than 300N.
5. alkali-free glass substrate as claimed in claim 3, wherein, described alkali-free glass substrate is by using a diameter of 30mm, R
The mean fracture load measured for ball (BOR) method of the ring of 2.5mm and the ball of a diameter of 10mm is scaled with the thickness of slab of 0.4mm
More than 300N.
6. a thining method for alkali-free glass substrate, wherein,
Described alkali-free glass substrate is following alkali-free glass, contains being impregnated into by least one interarea of described alkali-free glass substrate
Unit are and the stripping quantity of unit interval when having in the etching solution of Fluohydric acid. (HF) reach 0.17 (mg/cm2)/minute more than
Under conditions of, more than thinning for described alkali-free glass substrate 5 μm, described etching solution is 25 DEG C, the HF aqueous solution of 5%,
The strain point of described alkali-free glass is more than 710 DEG C, and glass viscosity reaches 102Temperature T during dPa s2Be 1710 DEG C with
Under, glass viscosity reaches 104Temperature T during dPa s4It is less than 1320 DEG C, contains in terms of based on oxide mole of %:
MgO+CaO+SrO+BaO is 17～21,
MgO/ (MgO+CaO+SrO+BaO) is more than 0.40,
MgO/ (MgO+CaO) is more than 0.40,
MgO/ (MgO+SrO) is more than 0.60.
7. a thining method for alkali-free glass substrate, wherein,
Described alkali-free glass substrate is following alkali-free glass, contains being impregnated into by least one interarea of described alkali-free glass substrate
Unit are and the stripping quantity of unit interval when having in the etching solution of Fluohydric acid. (HF) reach 0.17 (mg/cm2)/minute more than
Under conditions of, more than thinning for described alkali-free glass substrate 5 μm, described etching solution is 25 DEG C, the HF aqueous solution of 5%,
The strain point of described alkali-free glass is more than 710 DEG C, and glass viscosity reaches 102Temperature T during dPa s2Be 1710 DEG C with
Under, glass viscosity reaches 104Temperature T during dPa s4It is less than 1320 DEG C, contains in terms of based on oxide mole of %:
MgO+CaO+SrO+BaO is more than 18.2 and is less than 21,
MgO/ (MgO+CaO+SrO+BaO) is more than 0.25,
MgO/ (MgO+CaO) is more than 0.3,
MgO/ (MgO+SrO) is more than 0.60,
Al2O3× (MgO/ (MgO+CaO+SrO+BaO)) is more than 5.5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012124760 | 2012-05-31 | ||
| JP2012-124760 | 2012-05-31 | ||
| PCT/JP2013/065049 WO2013180220A1 (en) | 2012-05-31 | 2013-05-30 | Alkali-free glass substrate and method for reducing thickness of alkali-free glass substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104334507A CN104334507A (en) | 2015-02-04 |
| CN104334507B true CN104334507B (en) | 2016-11-30 |
Family
ID=
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1045422A (en) * | 1996-07-29 | 1998-02-17 | Asahi Glass Co Ltd | Alkali-free glass and flat display panel |
| CN1285325A (en) * | 1999-08-21 | 2001-02-28 | 肖特玻璃制造厂 | Aluminiu, boron silicate glass without alkali and application thereof |
| CN1525945A (en) * | 2001-03-24 | 2004-09-01 | Ф�ز������쳧 | Aluminoborosilicate glass devoid of alkali and uses thereof |
| WO2011001920A1 (en) * | 2009-07-02 | 2011-01-06 | 旭硝子株式会社 | Alkali-free glass and method for producing same |
| CN102076625A (en) * | 2008-06-25 | 2011-05-25 | 旭硝子株式会社 | Method for etching alkali-free glass substrate and display device |
| CN102417297A (en) * | 2010-09-27 | 2012-04-18 | 旭硝子株式会社 | Alkali-free glass and flat display panel |
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1045422A (en) * | 1996-07-29 | 1998-02-17 | Asahi Glass Co Ltd | Alkali-free glass and flat display panel |
| CN1285325A (en) * | 1999-08-21 | 2001-02-28 | 肖特玻璃制造厂 | Aluminiu, boron silicate glass without alkali and application thereof |
| CN1525945A (en) * | 2001-03-24 | 2004-09-01 | Ф�ز������쳧 | Aluminoborosilicate glass devoid of alkali and uses thereof |
| CN102076625A (en) * | 2008-06-25 | 2011-05-25 | 旭硝子株式会社 | Method for etching alkali-free glass substrate and display device |
| WO2011001920A1 (en) * | 2009-07-02 | 2011-01-06 | 旭硝子株式会社 | Alkali-free glass and method for producing same |
| CN102417297A (en) * | 2010-09-27 | 2012-04-18 | 旭硝子株式会社 | Alkali-free glass and flat display panel |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102371999B1 (en) | Non-alkali glass | |
| CN104350018B (en) | Alkali-free glass and the alkali-free glass plate for having used the alkali-free glass | |
| CN104364214B (en) | Alkali-free glass and method for producing same | |
| CN104271526B (en) | Alkali-free glass and manufacture method thereof | |
| CN103261109B (en) | Alkali-free glass and the manufacture method of alkali-free glass | |
| TWI603934B (en) | Alkali-free glass substrate, and alkali-free glass substrate thinning method | |
| CN104854050B (en) | Alkali-free glass substrate | |
| CN103080032B (en) | Flat panel display glass substrate and manufacture method thereof | |
| CN102471134A (en) | Alkali-free glass and method for producing same | |
| CN105722800B (en) | The manufacturing method of plate glass | |
| CN104302590A (en) | Method for producing plate glass | |
| TWI652243B (en) | Alkali-free glass | |
| JP6447510B2 (en) | Non-alkali glass substrate and method for thinning alkali-free glass substrate | |
| CN105555725B (en) | Alkali-free glass | |
| CN104334507B (en) | Alkali-free glass substrate and the thining method of alkali-free glass substrate | |
| CN106458701B (en) | Alkali-free glass | |
| CN103282319B (en) | Alkali-free glass and the manufacture method of alkali-free glass | |
| CN103282319A (en) | Non-alkali glass, and process for production of non-lkali glass |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Tokyo, Japan Patentee after: AGC Corporation Address before: Tokyo, Japan Patentee before: Asahi Glass Co., Ltd. |