WO2023037951A1 - 無アルカリガラス - Google Patents
無アルカリガラス Download PDFInfo
- Publication number
- WO2023037951A1 WO2023037951A1 PCT/JP2022/032891 JP2022032891W WO2023037951A1 WO 2023037951 A1 WO2023037951 A1 WO 2023037951A1 JP 2022032891 W JP2022032891 W JP 2022032891W WO 2023037951 A1 WO2023037951 A1 WO 2023037951A1
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- WO
- WIPO (PCT)
- Prior art keywords
- less
- glass
- alkali
- mgo
- cao
- Prior art date
Links
- 239000011521 glass Substances 0.000 title claims abstract description 272
- 238000004031 devitrification Methods 0.000 claims abstract description 44
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 31
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 238000000465 moulding Methods 0.000 claims description 10
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 238000006124 Pilkington process Methods 0.000 claims description 4
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- 238000007500 overflow downdraw method Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 22
- 239000004973 liquid crystal related substance Substances 0.000 description 14
- 230000007423 decrease Effects 0.000 description 13
- 239000010408 film Substances 0.000 description 13
- 239000013078 crystal Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005755 formation reaction Methods 0.000 description 7
- 239000006060 molten glass Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 230000035939 shock Effects 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 229910005793 GeO 2 Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- -1 that is Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000006355 external stress Effects 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 238000005816 glass manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-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
- 206010040925 Skin striae Diseases 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000310 actinide oxide Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 239000003258 bubble free glass Substances 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000006063 cullet Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 1
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium (III) oxide Inorganic materials [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- C03C3/087—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 containing calcium oxide, e.g. common sheet or container glass
-
- 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
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- 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
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
-
- 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
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
-
- 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
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
- C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
Definitions
- the present invention relates to an alkali-free glass that is suitable as a glass plate for various displays, photomasks, electronic device supports, information recording media, and the like.
- glass used in glass plates for various displays, photomasks, electronic device supports, and information recording media especially glass plates on which a thin film such as a metal or oxide is formed on the surface, has the following (1) to ( 4) and other characteristics are required.
- the glass when the glass contains an alkali metal oxide, the glass should be substantially free of alkali metal ions, because the alkali metal ions diffuse into the thin film and degrade the film properties of the thin film.
- the glass sheet When the glass sheet is exposed to high temperatures in the thin film formation process, the glass sheet should have a high strain point so as to minimize deformation of the glass sheet and shrinkage (thermal contraction) associated with structural stabilization of the glass.
- BHF buffered hydrofluoric acid
- ITO various acids used for etching metal electrodes
- resist stripper alkalis etc.
- the viscosity of the glass particularly the temperature T2 at which the glass viscosity is 10 2 dPa s and the temperature T 4 at which the glass viscosity is 10 4 dPa s should be lowered, and the glass surface devitrification temperature is required to be low and the strain point is not excessively increased.
- the glass described in Patent Documents 1 and 2 has a low Young's modulus and a low specific elastic modulus, so the self-weight deflection cannot be sufficiently reduced, or the Young's modulus is high and the specific elastic modulus is high, but the average thermal expansion coefficient is high. Therefore, the thermal shock resistance was low, and it was difficult to satisfy these requirements.
- An object of the present invention is to solve the above-mentioned drawbacks and to provide a glass that can reduce the self-weight deflection of the glass, has excellent thermal shock resistance, has excellent moldability, and places a low burden on glass manufacturing equipment.
- the specific elastic modulus is 36 MN ⁇ m/kg or more, SiO 2 55% or more and 80% or less in mol% display based on oxides, Al 2 O 3 12% or more and 20% or less, B 2 O 3 0.3% or more and 5% or less, MgO 5% or more and 18% or less, CaO 0.1% or more and 12% or less, SrO 0.1% or more and 8% or less, BaO contains 0% or more and 6% or less, MgO + CaO + SrO + BaO is 20% or less, MgO/CaO is 1 or more, MgO/(MgO+CaO+SrO+BaO) is 0.5 or more, MgO + Al 2 O 3 is 24% or more and 38% or less, (-3.125 ⁇ [SiO 2 ]-2.394 ⁇ [Al 2 O 3 ]-3.511 ⁇ [B 2 O 3 ]-2.167 ⁇ [MgO]-2.608 ⁇ [CaO] ⁇ 3.161 ⁇ [SrO
- Formula (II) is converted to (0.213 ⁇ [SiO 2 ]+1.006 ⁇ [Al 2 O 3 ] ⁇ 0.493 ⁇ [B 2 O 3 ]+1.158 ⁇ [MgO]+1.386 ⁇ [ CaO] + 3.092 ⁇ [SrO] + 4.198 ⁇ [BaO] + 2.004 ⁇ 10 2 ), the value of formula (I) / formula (II) ⁇ 100 is 36 or more, in [1] Alkali-free glass as described. [3] The alkali-free glass according to [1] or [2], wherein (MgO+CaO)/(SrO+BaO) is 8 or more.
- [7] The alkali-free glass according to any one of [1] to [6], which has a glass surface devitrification viscosity of 10 3.4 dPa ⁇ s or more.
- [8] The alkali-free glass according to any one of [1] to [7], containing 0 to 1% ZrO 2 in mol% based on oxides.
- [9] The alkali-free glass according to any one of [1] to [8], wherein the total amount of Li 2 O, Na 2 O and K 2 O is 0.2% or less in terms of mol% based on oxides. .
- the present invention it is possible to provide glass that can reduce the deflection under its own weight, has excellent thermal shock resistance, excellent moldability, and places a low burden on glass manufacturing equipment.
- composition range of each component of the glass is indicated by mol % based on oxides.
- the alkali-free glass of the present embodiment contains 55% or more and 80% or less of SiO 2 . If the content of SiO 2 is less than 55 mol % (hereinafter simply referred to as %), the strain point is not sufficiently raised, the average coefficient of thermal expansion tends to increase, and the density tends to increase. Therefore, the content of SiO 2 is 55% or more, preferably 58% or more, more preferably 60% or more, even more preferably 61% or more, particularly preferably 62% or more, and most preferably 63% or more. If the SiO 2 content exceeds 80%, the meltability of the glass tends to decrease, the Young's modulus tends to decrease, and the glass surface devitrification temperature (T c ) tends to increase. Therefore, the content of SiO 2 is 80% or less, preferably 75% or less, more preferably 73% or less, even more preferably 70% or less, particularly preferably 69% or less, and most preferably 68% or less.
- the alkali-free glass of this embodiment contains 12% or more and 20% or less of Al 2 O 3 .
- Al 2 O 3 increases the Young's modulus to suppress deflection, suppresses the phase separation of the glass, improves the fracture toughness value, and increases the strength of the glass. If the content of Al 2 O 3 is less than 12%, these effects are difficult to appear, and other components that increase the average thermal expansion coefficient are relatively increased. tend to be large. Therefore, the content of Al 2 O 3 is 12% or more, preferably 12.3% or more, more preferably 12.6% or more, even more preferably 13% or more, even more preferably 13.3% or more, Especially preferably 13.6% or more, most preferably 14% or more.
- the content of Al 2 O 3 exceeds 20%, the melting property of the glass may deteriorate, the strain point may be raised, and the glass surface devitrification temperature (T c ) may be raised. Therefore, the content of Al 2 O 3 is 20% or less, preferably 18% or less, more preferably 17.5% or less, even more preferably 17% or less, even more preferably 16.5% or less, particularly preferably is 16% or less, most preferably 15.5% or less.
- the alkali-free glass of the present embodiment contains 0.3% or more and 5% or less of B 2 O.
- B 2 O 3 improves resistance to buffered hydrofluoric acid (a mixed solution of hydrofluoric acid and ammonium fluoride, also called BHF), improves the dissolution reactivity of glass, and reduces the glass surface devitrification temperature (T c ) can be contained at 5% or less.
- the content of B 2 O 3 is preferably 4% or less, more preferably 3.5% or less, still more preferably 3% or less, particularly preferably 2.5% or less, and most preferably 2% or less. If the content of B 2 O 3 is less than 0.3%, these effects are difficult to appear. Therefore, the content of B 2 O 3 is 0.3% or more, preferably 0.5% or more, more preferably 0.6% or more, still more preferably 0.7% or more, and particularly preferably 0.8%. % or more, most preferably 0.9% or more.
- the alkali-free glass of this embodiment contains 5% or more and 18% or less of MgO. Since MgO increases the Young's modulus without increasing the density, by increasing the specific elastic modulus, the problem of self-weight deflection can be reduced, and the fracture toughness value is improved to increase the glass strength. MgO also improves solubility. If the content of MgO is less than 5%, these effects are difficult to obtain and the coefficient of thermal expansion may become too low. Therefore, the content of MgO is 5% or more.
- the content of MgO is preferably 7% or more, more preferably 9% or more, still more preferably 10% or more, particularly preferably 10.5% or more, and most preferably 11% or more.
- the MgO content is 18% or less, preferably 17.5% or less, more preferably 17% or less, even more preferably 16.5% or less, particularly preferably 16.3% or less, most preferably 16% or less. % or less.
- the alkali-free glass of this embodiment contains 0.1% or more and 12% or less of CaO.
- CaO has the characteristic of increasing the specific modulus next to MgO among the alkaline earth metals and not excessively lowering the strain point, and also improves the solubility like MgO. Furthermore, it also has the feature that the glass surface devitrification temperature (T c ) is less likely to be increased than with MgO. If the CaO content is less than 0.1%, these effects are less likely to appear. Therefore, the content of CaO is 0.1% or more.
- the CaO content is preferably 0.5% or more, more preferably 1% or more, still more preferably 1.5% or more, particularly preferably 2% or more, and most preferably 2.5% or more.
- the CaO content is 12% or less, preferably 10% or less, more preferably 9% or less, even more preferably 8.5% or less, particularly preferably 8% or less, and most preferably 7.5% or less. is.
- the alkali-free glass of this embodiment contains 0.1% or more and 8% or less of SrO.
- SrO does not increase the glass surface devitrification temperature (T c ) and improves the solubility, but if the SrO content is less than 0.1%, these effects are less likely to appear. Therefore, the SrO content is 0.1% or more, preferably 0.15% or more, more preferably 0.2% or more, still more preferably 0.3% or more, and particularly preferably 0.4% or more. be.
- SrO has a lower effect than BaO, and if the SrO content exceeds 8%, the effect of increasing the density becomes more dominant when the SrO content is too high, and the average coefficient of thermal expansion becomes too high. Therefore, the SrO content is 8% or less, preferably 6% or less, more preferably 5% or less, even more preferably 4% or less, particularly preferably 3% or less, and most preferably 2% or less.
- the alkali-free glass of this embodiment contains 0% or more and 6% or less of BaO.
- BaO can be contained in order to improve the solubility without increasing the glass surface devitrification temperature (T c ).
- the content of BaO is preferably 0.1% or more, more preferably 0.3% or more, still more preferably 0.5% or more, particularly preferably 0.8% or more, Most preferably it is 1% or more. If a large amount of BaO is contained, the density tends to increase, the Young's modulus tends to decrease, and the average coefficient of thermal expansion tends to increase too much.
- the BaO content is 6% or less, preferably 5.5% or less, more preferably 5% or less, particularly preferably 4.5% or less, and most preferably 4% or less.
- substantially no BaO is preferably contained. “Substantially free” means not containing excluding unavoidable impurities, and in the present embodiment, the content of BaO is, for example, less than 0.1%, preferably less than 0.05%, more Preferably, it is 0.01% or less.
- MgO + CaO + SrO + BaO is 20% or less, preferably 19.8% or less, more preferably 19.6% or less, still more preferably 19.4% or less, particularly preferably 19.2% or less, most preferably 19.2% or less. 1% or less.
- T c glass surface devitrification temperature
- MgO + CaO + SrO + BaO is preferably 10% or more, more preferably 12% or more, still more preferably 13% or more, even more preferably 14% or more, particularly preferably 15%. above, and most preferably above 16%.
- MgO+CaO+SrO+BaO is, for example, 10% or more and 20% or less.
- MgO/CaO is set to 1 or more.
- MgO/CaO is preferably 1.1 or more, more preferably 1.2 or more, still more preferably 1.3 or more, particularly preferably 1.5 or more, most preferably 1.8 or more.
- MgO/CaO is preferably 100 or less, more preferably 30 or less, still more preferably 15 or less, particularly preferably 10 or less, most preferably 5 or less.
- MgO/CaO is 1 or more and 100 or less, for example.
- MgO/(MgO+CaO+SrO+BaO) is set to 0.5 or more.
- MgO/(MgO+CaO+SrO+BaO) is preferably 0.52 or more, more preferably 0.54 or more, even more preferably 0.56 or more, particularly preferably 0.58 or more, and most preferably 0.6 or more.
- MgO/(MgO+CaO+SrO+BaO) is preferably 0.95 or less, more preferably 0.95 or less. It is 9 or less, more preferably 0.85 or less, and particularly preferably 0.8 or less.
- MgO/(MgO+CaO+SrO+BaO) is, for example, 0.5 or more and 0.95 or less.
- MgO+Al 2 O 3 the total amount of MgO and Al 2 O 3 , that is, MgO+Al 2 O 3 is 24% or more and 38% or less. If the MgO+Al 2 O 3 content is less than 24%, the Young's modulus is low and the deformation of the substrate against external stress is large. Therefore, MgO+Al 2 O 3 is made 24% or more. MgO+Al 2 O 3 is preferably 24.2% or more, more preferably 24.5% or more, even more preferably 25% or more, particularly preferably 25.5% or more, most preferably 26% or more. On the other hand, if the MgO+Al 2 O 3 content exceeds 38%, the devitrification temperature rises and the formability deteriorates.
- MgO+Al 2 O 3 is made 38% or less.
- MgO+Al 2 O 3 is preferably 35% or less, more preferably 33% or less, still more preferably 32% or less, particularly preferably 31% or less, and most preferably 30% or less.
- (MgO+CaO)/(SrO+BaO) is 200 or less, the increase in devitrification temperature can be suppressed, which is preferable.
- (MgO+CaO)/(SrO+BaO) is preferably 100 or less, more preferably 75 or less, even more preferably 60 or less, and particularly preferably 50 or less.
- (MgO+CaO)/(SrO+BaO) is, for example, 8 or more and 200 or less.
- the value represented by formula (I) is preferably 90.5 or more and 97 or less, more preferably 90.8 or more and 95 or less, still more preferably 91 or more and 94 or less, particularly preferably 91.2 or more and 93.5 or less, Most preferably, it is 91.5 or more and 93 or less.
- the description of [metal oxide] in the formula represents the numerical value when the metal oxide component is expressed in mol% (same in the description of other parts of this specification .). For example, when SiO 2 is 60 mol % in terms of mol % based on oxide, [SiO 2 ] represents 60.
- the alkali-free glass of the present embodiment has formula (II) as (0.213 ⁇ [SiO 2 ]+1.006 ⁇ [Al 2 O 3 ] ⁇ 0.493 ⁇ [B 2 O 3 ]+1.158 ⁇ [MgO ]+1.386 ⁇ [CaO]+3.092 ⁇ [SrO]+4.198 ⁇ [BaO]+2.004 ⁇ 10 2 ), the value of formula (I)/formula (II) ⁇ 100 is 36 or more.
- the value represented by formula (I)/formula (II) ⁇ 100 is an index of specific elastic modulus. It is preferable that the value represented by formula (I)/formula (II) ⁇ 100 is 36 or more because the specific elastic modulus increases.
- the value of formula (I)/formula (II) ⁇ 100 is more preferably 36.1 or more, still more preferably 36.2 or more, even more preferably 36.3 or more, particularly preferably 36.4 or more, and most preferably is greater than or equal to 36.5. It is preferable that the value of formula (I)/formula (II) ⁇ 100 is 50 or less because the cutting margin can be maintained. Here, the value of formula (I)/formula (II) ⁇ 100 is, for example, 36 or more and 50 or less.
- the value represented by the formula (II) is an index of density, and a value of 260 or less is preferable because the density becomes low. If the value represented by formula (II) is less than 240, the density may become too low. Therefore, 240 or more is preferable.
- the value represented by formula (II) is more preferably 242 or more and 259 or less, still more preferably 244 or more and 258 or less, even more preferably 246 or more and 257 or less, particularly preferably 248 or more and 256 or less, and most preferably 250 or more and 255 or less. is.
- the alkali-free glass of the present embodiment preferably does not substantially contain alkali metal oxides such as Li2O , Na2O and K2O .
- substantially free of alkali metal oxides means that it does not contain anything other than unavoidable impurities mixed in from raw materials or the like, that is, it does not contain it intentionally.
- the content is 0.1% or less, preferably 0.08% or less, more preferably 0.05% or less, still more preferably 0.03% or less.
- the alkali-free glass of the present embodiment is P 2 It is preferably substantially free of O5 .
- substantially free of P 2 O 5" means, for example, the content is 0.1% or less.
- the alkali-free glass of the present embodiment does not substantially contain PbO, As2O3 , and Sb2O3 .
- substantially free of PbO, As2O3, and Sb2O3 means that the content of PbO, As2O3, and Sb2O3 is , for example , 0.01 % or less . , preferably 0.005% or less.
- one or more of As 2 O 3 and Sb 2 O 3 may be contained in a total amount of 1% or less, preferably 0.5%, in order to improve the meltability, clarity, moldability, etc. of the glass. It is 5% or less, more preferably 0.3% or less, still more preferably 0.2% or less, particularly preferably 0.15% or less, and most preferably 0.1% or less.
- the alkali-free glass of the present embodiment contains one of ZrO 2 , ZnO, Fe 2 O 3 , SO 3 , F, Cl, and SnO 2 in order to improve the meltability, clarity, formability, etc. of the glass.
- the above may be contained in a total amount of 2% or less. It is preferably 1% or less, more preferably 0.5% or less.
- the alkali-free glass of the present embodiment may contain ZrO 2 , for example, 0.001% or more, in order to lower the melting temperature of the glass, increase the Young's modulus, and improve the chemical resistance. good.
- ZrO 2 for example, 0.001% or more
- the content of ZrO2 is preferably 1% or less, more preferably 0.5% or less, still more preferably 0.2% or less, still more preferably 0.1% or less, and even more preferably 0.05%.
- substantially free of ZrO 2 means that it does not contain anything other than unavoidable impurities mixed in from raw materials or the like, that is, it does not contain ZrO 2 intentionally. In the present embodiment, substantially free of ZrO 2 means that the content of ZrO 2 is, for example, 0.01% or less, preferably 0.005% or less.
- the alkali-free glass of the present embodiment may contain 0% or more and 0.5% or less of SnO 2 in order to improve the meltability and clarity of the glass.
- the SnO2 content is preferably 0.4% or less, more preferably 0.3% or less.
- the alkali-free glass of this embodiment may contain F in order to improve the solubility and clarity of the glass.
- F is contained, the content of F is preferably 1% or less, more preferably 0.5% or less, still more preferably 0.4% or less, and even more preferably 0.3% or less in terms of mol%. More preferably 0.2% or less, particularly preferably 0.1% or less.
- the content of F is the amount remaining in the molten glass, not the amount added in the glass raw material. This also applies to the Cl content, which will be described later.
- the alkali-free glass of the present embodiment may contain 0.001% or more and 0.05% or less of Fe in terms of Fe 2 O 3 in order to improve the meltability of the glass.
- Lowering the Fe content of the glass reduces the infrared absorption by Fe 2+ during the melting process, resulting in an increase in the thermal conductivity of the glass.
- a heat ray such as a burner flame in a glass melting furnace
- the temperature distribution of the molten glass becomes smaller, the convection speed of the molten glass decreases, and the foam quality and homogeneity of the glass product deteriorate. It may get worse.
- the Fe content is 0.001% or more in terms of Fe 2 O 3 , the above problems are less likely to occur. Clarity and homogeneity depend on sufficient convection of molten glass. When it is desired to improve the solubility of the glass, the Fe content is more preferably 0.002% or more, still more preferably 0.005% or more, even more preferably 0.008% or more in terms of Fe 2 O 3 , 0.01% or more is particularly preferable, 0.02% or more is still more preferable, 0.03% or more is particularly preferable, and 0.04% or more is most preferable.
- the Fe content of the glass increases, Fe exists as Fe 2+ or Fe 3+ in the glass, which may reduce the transmittance of the glass.
- Fe 3+ has absorption in the wavelength range of 300 nm or less, the UV transmittance of the glass may decrease.
- the two glass substrates constituting the flat panel display are made of a photocurable resin. It is preferable because it is possible to bond together.
- the Fe content is preferably 0.05% or less, more preferably 0.04% or less in terms of Fe 2 O 3 .
- 0.03% or less is more preferable, 0.02% or less is even more preferable, 0.01% or less is even more preferable, 0.008% or less is even more preferable, 0.006% or less is even more preferable, and 0 0.004% or less is particularly preferred, and 0.002% or less is most preferred.
- Cl may be contained in an amount of 0.1% or more and 1.0% or less in terms of mol%.
- the Cl content is preferably 0.15% or more, more preferably 0.2% or more, even more preferably 0.25% or more, and particularly preferably 0.3% or more.
- the Cl content is 1.0% or less, the effect of suppressing the enlargement of the bubble layer during glass production is good. It is preferably 0.8% or less, more preferably 0.6% or less.
- the alkali-free glass contains one or more of Se 2 O 3 , TeO 2 , Ga 2 O 3 , In 2 O 3 , GeO 2 , CdO, BeO and Bi 2 O 3 in a total amount of 2% or less. preferably 1% or less, more preferably 0.5% or less, still more preferably 0.3% or less, still more preferably 0.1% or less, particularly preferably 0.05% or less, most preferably 0.5% or less. 01% or less.
- the GeO2 content is preferably less than 0.1%, more preferably 0.08% or less, even more preferably 0.05% or less, even more preferably 0.03% or less, particularly preferably 0.01% or less , is most preferably substantially free.
- “Substantially free of GeO 2” means that it does not contain anything other than unavoidable impurities mixed in from raw materials or the like, that is, it does not contain GeO 2 intentionally.
- “substantially free of GeO 2 ” means that the content of GeO 2 is, for example, 0.05% or less, preferably 0.01% or less, and more preferably 0.005% or less.
- the alkali-free glass of the present embodiment may contain rare earth oxides and transition metal oxides in order to improve the meltability, clarity, moldability, etc. of the glass, and to improve the hardness of the glass, such as Young's modulus.
- the alkali-free glass of the present embodiment contains Sc2O3 , Y2O3 , La2O3 , Ce2O3 , CeO2 , Pr2O3 , Nd2O3 , Pm2O as rare earth oxides . 3 , Sm2O3 , Eu2O3 , Gd2O3 , Tb2O3 , Dy2O3 , Ho2O3 , Er2O3 , Tm2O3 , Yb2O3 and Lu2O 3 may be contained in a total amount of 2% or less, preferably 1% or less, more preferably 0.5% or less, even more preferably 0.3% or less, even more preferably 0.3% or less.
- La 2 O 3 content is preferably less than 1%, more preferably 0.5% or less, even more preferably 0.3% or less, even more preferably 0.1% or less, particularly preferably 0.05% or less , is most preferably substantially free.
- substantially free of La 2 O 3 means that it does not contain anything other than unavoidable impurities mixed from raw materials or the like, that is, it does not contain it intentionally.
- substantially free of La 2 O 3 means that the content of La 2 O 3 is, for example, less than 0.05%, preferably 0.01% or less, more preferably 0.005%. It is below.
- the alkali-free glass of the present embodiment contains, as transition metal oxides, one or more of V 2 O 5 , Ta 2 O 3 , Nb 2 O 5 , WO 3 , MoO 3 and HfO 2 in a total amount of 2%. It may contain the following, preferably 1% or less, more preferably 0.5% or less, still more preferably 0.3% or less, even more preferably 0.1% or less, particularly preferably 0.05% or less, Most preferably, it is 0.01% or less.
- the alkali-free glass of the present embodiment may contain 2% or less, preferably 1% or less, more preferably 0.5% of ThO 2 , which is an actinide oxide. 0.3% or less, still more preferably 0.1% or less, even more preferably 0.05% or less, particularly preferably 0.01% or less, most preferably 0.005% or less .
- the alkali-free glass of the present embodiment preferably has a ⁇ -OH value of 0.05 mm ⁇ 1 or more and 0.6 mm ⁇ 1 or less, because the heat shrinkage of the glass is suppressed.
- the ⁇ -OH value is an index of the water content in glass.
- the absorbance of a glass sample to light with a wavelength of 2.75 to 2.95 ⁇ m is measured, and the maximum absorbance value ⁇ max is measured by the thickness (mm ).
- the ⁇ -OH value of the glass is more preferably 0.45 mm ⁇ 1 or less, more preferably 0.4 mm ⁇ 1 or less, even more preferably 0.35 mm ⁇ 1 or less, even more preferably 0.3 mm ⁇ 1 or less, and more It is more preferably 0.28 mm -1 or less, particularly preferably 0.25 mm -1 or less, and most preferably 0.23 mm -1 or less.
- the ⁇ -OH value is 0.05 mm ⁇ 1 or more, it is easy to achieve the strain point of the glass described later.
- the ⁇ -OH value is more preferably 0.08 mm ⁇ 1 or more, still more preferably 0.1 mm ⁇ 1 or more, even more preferably 0.13 mm ⁇ 1 or more, and even more preferably 0.15 mm ⁇ 1 or more. , particularly preferably 0.18 mm ⁇ 1 or more, most preferably 0.2 mm ⁇ 1 or more.
- the alkali-free glass of this embodiment has a strain point of 700° C. or higher and 740° C. or lower. If the strain point is less than 700° C., deformation of the glass plate and shrinkage (thermal contraction) due to structural stabilization of the glass are likely to occur when the glass plate is exposed to high temperatures in the thin film formation process of the display.
- the strain point is preferably 705° C. or higher, more preferably 710° C. or higher, even more preferably 715° C. or higher, particularly preferably 720° C. or higher, most preferably 725° C. or higher.
- the strain point is too high, the temperature of the slow cooling device needs to be raised correspondingly, and the life of the slow cooling device tends to be shortened. Therefore, it is 740° C. or less.
- the strain point is preferably 738°C or lower, more preferably 736°C or lower, and even more preferably 735°C or lower.
- the alkali-free glass of this embodiment has a density of 2.6 g/cm 3 or less.
- the density is preferably 2.59 g/cm 3 or less, more preferably 2.58 g/cm 3 or less, still more preferably 2.57 g/cm 3 or less, particularly preferably 2.56 g/cm 3 or less, most preferably 2.56 g/cm 3 or less. 55 g/cm 3 or less.
- the large substrate is, for example, a substrate having at least one side of 1800 mm or more.
- Density is more preferably 2.42 g/cm 3 or higher, still more preferably 2.44 g/cm 3 or higher, even more preferably 2.46 g/cm 3 or higher, particularly preferably 2.48 g/cm 3 or higher, most preferably 2.5 g/cm 3 or more.
- the density is, for example, 2.4 g/cm 3 or more and 2.6 g/cm 3 or less.
- the Young's modulus of the alkali-free glass of this embodiment is 90 GPa or more and 100 GPa or less.
- the Young's modulus is 90 GPa or more, deformation of the substrate due to external stress is suppressed.
- warping of the substrate can be suppressed.
- warpage of the substrate is suppressed when a gate metal film such as copper or a gate insulating film such as silicon nitride is formed on the surface of the substrate in the manufacture of a TFT-side substrate for a flat panel display.
- deflection when the size of the substrate is increased is also suppressed.
- Young's modulus is preferably 90.5 GPa or higher, more preferably 91 GPa or higher, still more preferably 91.2 GPa or higher, particularly preferably 91.5 GPa or higher, and most preferably 92 GPa or higher. When the Young's modulus is 100 GPa or less, the cutting margin becomes large. Young's modulus is preferably 98 GPa or less, more preferably 97 GPa or less, still more preferably 96 GPa or less, and most preferably 95 GPa or less. Young's modulus can be measured by an ultrasonic method.
- the alkali-free glass of this embodiment has an average thermal expansion coefficient of 30 ⁇ 10 ⁇ 7 /K or more at 50 to 350° C. If it is less than 30 ⁇ 10 ⁇ 7 /K, for example, in the production of a TFT-side substrate for a flat panel display, a gate metal film such as copper and a gate insulating film such as silicon nitride are laminated in order on non-alkali glass. However, the thermal expansion difference with the gate metal film such as copper formed on the substrate surface becomes large, and there is a possibility that problems such as substrate warpage and film peeling may occur. The average thermal expansion coefficient at 50 to 350° C.
- the glass is preferably 30.5 ⁇ 10 ⁇ 7 /K or more, more preferably 31 ⁇ 10 ⁇ 7 /K or more, still more preferably 31.5 ⁇ 10 ⁇ 7 /K or more, Especially preferably 32 ⁇ 10 ⁇ 7 /K or more, most preferably 32.5 ⁇ 10 ⁇ 7 /K or more.
- the average thermal expansion coefficient at 50 to 350° C. exceeds 39 ⁇ 10 ⁇ 7 /K, the glass may break during the manufacturing process of products such as displays, and the thermal shock resistance of the glass will be low. Therefore, it is 39 ⁇ 10 ⁇ 7 /K or less.
- the average thermal expansion coefficient at 50 to 350° C. is, for example, 30 ⁇ 10 ⁇ 7 /K or more and 39 ⁇ 10 ⁇ 7 /K or less.
- T2 is 1590°C or higher, SO3 can be used as a refining agent in the glass manufacturing process.
- T2 is preferably 1592°C or higher, more preferably 1594°C or higher, even more preferably 1596°C or higher, particularly preferably 1598°C or higher, and most preferably 1600°C or higher.
- T2 is 1690°C or less, the melting property of the glass is excellent. Therefore, the burden on manufacturing equipment can be reduced.
- T2 is preferably 1670°C or less, more preferably 1660°C or less, even more preferably 1650°C or less, even more preferably 1640°C or less, most preferably 1635°C or less.
- T4 is 1350°C or less
- the formability of the glass is excellent.
- by lowering the temperature during glass molding volatile substances in the atmosphere around the glass can be reduced, thereby reducing the defects of the glass. Since the glass can be molded at a low temperature, the burden on manufacturing equipment can be reduced. For example, the life of equipment such as a float bath for molding glass can be extended, and productivity can be improved.
- T4 is preferably 1340°C or lower, more preferably 1330°C or lower, even more preferably 1320°C or lower, even more preferably 1310°C or lower, particularly preferably 1300°C or lower, most preferably 1295°C or lower.
- the lower limit of T4 is not particularly limited, it is usually 1100°C or higher.
- T4 is, for example, 1100° C. or higher and 1350° C. or lower.
- T 2 and T 4 are determined by measuring the viscosity using a rotational viscometer according to the method specified in ASTM C 965-96, and the temperature at which the viscosity becomes 10 2 d ⁇ Pa ⁇ s is defined as T 2 and 10 4 d ⁇ The temperature when it becomes Pa ⁇ s can be obtained as T4 .
- NBS710 and NIST717a were used as reference samples for device calibration.
- the alkali-free glass of the present embodiment has a glass surface devitrification temperature (T c ) of less than T 4 +80°C.
- T c glass surface devitrification temperature
- T 4 +80° C. the formability of the glass is excellent. It is possible to suppress the decrease in transmittance due to the formation of crystals inside the glass during molding. Moreover, the burden on manufacturing facilities can be reduced. For example, the life of equipment such as a float bath for molding glass can be extended, and productivity can be improved.
- T c is preferably T 4 +75° C. or lower, more preferably T 4 +70° C. or lower, even more preferably T 4 +60° C. or lower, even more preferably T 4 +50° C. or lower, particularly preferably T 4 +40° C.
- T 4 +40° C. or lower Preferably, it is T 4 +30° C. or lower.
- Tc is, for example, 1000° C. or more and less than T 4 +80° C.
- the glass surface devitrification temperature (T c ) in the present embodiment can be obtained as follows. That is, crushed glass particles are placed in a platinum dish and heat treated for 17 hours in an electric furnace controlled at a constant temperature. The lowest temperature at which crystals do not precipitate is observed, and the average value is defined as the glass surface devitrification temperature (T c ).
- the alkali-free glass of the present embodiment preferably has a viscosity (glass surface devitrification viscosity ( ⁇ c )) at the glass surface devitrification temperature (T c ) of 10 3.4 dPa ⁇ s or more.
- a viscosity glass surface devitrification viscosity ( ⁇ c )
- T c glass surface devitrification temperature
- ⁇ c glass surface devitrification temperature
- the formability of the glass sheet is excellent.
- the burden on manufacturing facilities can be reduced. For example, it is possible to extend the life of equipment such as a float bath for molding into a glass plate, and to improve productivity.
- ⁇ c is more preferably 10 3.5 dPa ⁇ s or more, still more preferably 10 3.6 dPa ⁇ s or more, particularly preferably 10 3.7 dPa ⁇ s or more, and most preferably 10 3.8 dPa ⁇ s. s or more.
- the upper limit of ⁇ c is not particularly limited, it is usually 10 6 dPa ⁇ s or less.
- ⁇ c is, for example, 10 3.4 dPa ⁇ s or more and 10 6 dPa ⁇ s or less.
- the alkali-free glass of the present embodiment has a specific elastic modulus (Young's modulus (GPa)/density (g/cm 3 )) of 36 MN ⁇ m/kg or more.
- the specific elastic modulus is preferably 36.1 MN ⁇ m/kg or more, more preferably 36.2 MN ⁇ m/kg or more, still more preferably 36.3 MN ⁇ m/kg or more, and particularly preferably 36.4 MN ⁇ m/kg or more. , and most preferably 36.5 MN ⁇ m/kg or more.
- the upper limit of the specific elastic modulus is not particularly limited, it is usually 50 MN ⁇ m/kg or less.
- the specific elastic modulus is, for example, 36 MN ⁇ m/kg or more and 50 MN ⁇ m/kg or less.
- the large substrate is, for example, a substrate having at least one side of 1800 mm or more. At least one side of the large substrate may be, for example, 2000 mm or longer, 2500 mm or longer, 3000 mm or longer, or 3500 mm or longer.
- the alkali-free glass of the present embodiment preferably has a glass transition point (hereinafter also referred to as Tg) of 850°C or lower. If Tg is 850° C. or lower, the load on manufacturing equipment can be reduced. For example, the surface temperature of rolls used for molding glass can be lowered, the life of equipment can be extended, and productivity can be improved.
- Tg is more preferably 830° C. or lower, more preferably 820° C. or lower, even more preferably 810° C. or lower, and particularly preferably 800° C. or lower. From the viewpoint of heat resistance, Tg is preferably 730°C or higher. Tg is more preferably 740° C. or higher, more preferably 750° C. or higher, particularly preferably 760° C. or higher, and most preferably 770° C. or higher. Here, Tg is preferably 730° C. or higher and 850° C. or lower.
- the alkali-free glass of the present embodiment preferably has a photoelastic constant of 31 nm/MPa/cm or less. Due to the stress generated during the liquid crystal display panel manufacturing process or during the use of the liquid crystal display device, the glass substrate may have birefringence, black display may become gray, and the contrast of the liquid crystal display may decrease. This phenomenon can be suppressed if the photoelastic constant is 31 nm/MPa/cm or less.
- Photoelastic constant is more preferably 30 nm/MPa/cm or less, more preferably 29 nm/MPa/cm or less, even more preferably 28 nm/MPa/cm or less, particularly preferably 27.5 nm/MPa/cm or less, most preferably It is 27 nm/MPa/cm or less.
- the photoelastic constant is preferably 23 nm/MPa/cm or more, more preferably 25 nm/MPa/cm or more.
- the photoelastic constant can be measured at a measurement wavelength of 546 nm by the disc compression method.
- the photoelastic constant is preferably 23 nm/MPa/cm or more and 31 nm/MPa/cm or less.
- ⁇ is the average linear expansion coefficient at 50 to 350 ° C.
- E is the Young's modulus
- C is the photoelastic constant. and C is preferably 9.2 ⁇ 10 ⁇ 7 /K or less.
- the heat from the backlight makes the temperature distribution of the glass plate closer to the backlight (an array glass plate in a TFT-LCD) uneven. Assuming that the difference between the highest and lowest temperatures in the glass plate is ⁇ T, the maximum value F of stress generated in this glass plate is expressed by the following equation.
- ⁇ E ⁇ C is more preferably 9 ⁇ 10 ⁇ 7 /K or less, still more preferably 8.8 ⁇ 10 ⁇ 7 /K or less, even more preferably 8.7 ⁇ 10 ⁇ 7 /K or less, and particularly preferably is 8.6 ⁇ 10 ⁇ 7 /K or less, most preferably 8.5 ⁇ 10 ⁇ 7 /K or less.
- the lower limit of ⁇ E ⁇ C is not particularly limited, it is usually 5 ⁇ 10 ⁇ 7 /K or more.
- ⁇ E ⁇ C is preferably 5 ⁇ 10 ⁇ 7 /K or more and 9.2 ⁇ 10 ⁇ 7 /K or less.
- the alkali-free glass of the present embodiment has a Young's modulus as high as 90 GPa or more and a specific elastic modulus as high as 36 MN ⁇ m/kg or more, so self-weight deflection can be reduced. Therefore, it is suitable for a glass plate used as a large substrate.
- the large-sized substrate is suitable for, for example, a glass plate having at least one side of 1800 mm or more, and as a specific example, a glass plate having a long side of 1800 mm or more and a short side of 1500 mm or more.
- the alkali-free glass of the present embodiment is preferably a glass plate having at least one side of 2400 mm or more, for example, a glass plate having a long side of 2400 mm or more and a short side of 2100 mm or more, and a glass plate having at least one side of 3000 mm or more, for example, a long side of 3000 mm or more.
- a glass plate with a short side of 2800 mm or more particularly preferably for a glass plate with at least one side of 3200 mm or more, for example, a glass plate with a long side of 3200 mm or more and a short side of 2900 mm or more, and at least one side of 3300 mm or more, for example, It is most preferable for a glass plate having a long side of 3300 mm or more and a short side of 2950 mm or more.
- the thickness of the glass plate of the present embodiment is preferably 1 mm or less because weight reduction can be achieved.
- the thickness of the glass plate of the present embodiment is more preferably 0.7 mm or less, more preferably 0.65 mm or less, still more preferably 0.55 mm or less, particularly preferably 0.45 mm or less, and most preferably 0.4 mm or less. is.
- the glass plate of this embodiment can also have a thickness of 0.1 mm or less, or 0.05 mm or less. However, from the viewpoint of preventing self-weight deflection, the thickness is preferably 0.1 mm or more, more preferably 0.2 mm or more.
- the thickness of the glass plate is preferably 0.1 mm or more and 1 mm or less.
- the alkali-free glass of this embodiment can be produced, for example, by the following procedure.
- Raw materials of the above components are blended so as to have a target content in the glass composition, put into a melting furnace, heat to 1500 to 1800° C. and melt to obtain molten glass.
- the obtained molten glass is formed into a glass ribbon having a predetermined thickness by a forming apparatus, and the glass ribbon is annealed and cut to obtain an alkali-free glass.
- molten glass into a glass plate by a float method, a fusion method, or the like. It is preferable to use the float method from the viewpoint of stably producing a large glass plate having a high Young's modulus (for example, one side of 1800 mm or more).
- Examples will be described below, but the present invention is not limited to these examples.
- Examples 1-14 and 24-55 are working examples, and Examples 15-23 are comparative examples.
- Raw materials for each component were mixed so that the glass composition would be the target composition (unit: mol %) shown in Examples 1 to 55, and melted at 1600° C. for 1 hour using a platinum crucible. After melting, the melted liquid was poured onto a carbon plate, held at a temperature of (glass transition point +30°C) for 60 minutes, and then cooled to room temperature (25°C) at a rate of 1°C per minute to obtain a sheet glass. This was mirror-polished to obtain a glass plate, which was subjected to various evaluations.
- the ⁇ -OH value of the glass was obtained by the following procedure.
- ( ⁇ -OH value) The absorbance of the glass sample to light with a wavelength of 2.75 to 2.95 ⁇ m was measured, and the ⁇ -OH value was obtained by dividing the maximum absorbance value ⁇ max by the thickness (mm) of the sample. The results are shown in Tables 1-8. In Tables 1 to 8, values shown in parentheses are calculated values.
- the method for measuring each physical property is shown below.
- (Average coefficient of thermal expansion ⁇ ) It was measured using a differential thermal dilatometer (dilatometer) according to the method specified in JIS R3102 (1995). The measurement temperature range was from room temperature to 400° C. or higher, and the average thermal expansion coefficient at 50 to 350° C. was expressed in units of 10 ⁇ 7 /K.
- (density) According to the method specified in JIS Z 8807, about 20 g of a bubble-free glass lump was measured by the Archimedes method.
- (Strain point) It was measured by the fiber stretching method according to the method specified in JIS R3103-2 (2001).
- (Tg) It was measured by a thermal expansion method according to the method specified in JIS R3103-3 (2001).
- (Young's modulus) A glass having a thickness of 0.5 to 10 mm was measured by an ultrasonic pulse method according to the method specified in JIS Z 2280.
- T2 The viscosity was measured using a rotational viscometer according to the method specified in ASTM C 965-96, and the temperature T 2 (°C) at which 10 2 d ⁇ Pa ⁇ s was reached was measured.
- T4 The viscosity was measured using a rotational viscometer according to the method specified in ASTM C 965-96, and the temperature T 4 (°C) at which 10 4 d ⁇ Pa ⁇ s was reached was measured.
- T c Glass surface devitrification temperature The glass was pulverized and classified using a test sieve so that the particle size ranged from 2 to 4 mm.
- the obtained glass cullet was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, washed with deionized water, dried, placed in a platinum dish, and heat-treated in an electric furnace controlled at a constant temperature for 17 hours. did The heat treatment temperature was set at intervals of 10°C. After the heat treatment, the glass was removed from the platinum dish, and the maximum temperature at which crystals precipitated on the surface of the glass and the minimum temperature at which crystals did not precipitate were observed using an optical microscope. The maximum temperature at which crystals precipitate on the surface of the glass and the minimum temperature at which crystals do not precipitate were each measured once.
- Tc glass surface devitrification temperature
- Glass surface devitrification viscosity ⁇ c The glass surface devitrification temperature (T c ) was obtained by the method described above, and the viscosity of the glass at the glass surface devitrification temperature (T c ) was measured to obtain the glass surface devitrification viscosity ( ⁇ c ).
- the table below shows the logarithm value of the glass surface devitrification viscosity ( ⁇ c ).
- Specific modulus The specific elastic modulus was determined by dividing the Young's modulus determined by the procedure described above by the density.
- photoelastic constant The photoelastic constant was measured at a measurement wavelength of 546 nm by the disc compression method.
- BHF Haze If the haze change before and after the glass plate was immersed in a 19BHF solution at 25° C. for 20 minutes was 1% or less, it was evaluated as ⁇ , and if it exceeded 1%, it was evaluated as ⁇ .
- MgO+CaO+SrO+ BaO is 20% or less
- MgO/CaO is 1 or more
- MgO/(MgO+CaO+SrO+BaO) is 0.5 or more
- MgO+ Al2O3 is 24% or more and 38% or less
- the value of formula (I) is 90 or more and 100 or less.
- Examples 1 to 14 and 24 to 55 have a strain point of 700° C. or higher and 740° C. or lower, a density of 2.6 g/cm 3 or lower, a Young's modulus E of 90 GPa or higher and 100 GPa or lower, and an average thermal expansion coefficient ⁇ at 50 to 350° C.
- the glass viscosity is 10 2 dPa s . was 1350° C. or less, the difference (T c ⁇ T 4 ) between the glass surface devitrification temperature (T c ) and T 4 was less than 80° C., and the specific elastic modulus was 36 MN ⁇ m/kg or more. As described above, when the specific elastic modulus is 36 MN ⁇ m/kg or more, the self-weight deflection becomes small.
- Example 17 which does not contain B 2 O 3 and SrO and contains more than 20% MgO + CaO + SrO + BaO, has a high strain point of more than 740°C and a low temperature T2 at which the glass viscosity becomes 10 2 dPa s, which is less than 1590°C. .
- Example 18 containing no B 2 O 3 and SrO, less than 12% Al 2 O 3 content, and more than 20% MgO+CaO+SrO+BaO had a glass surface devitrification temperature (T c ) of T 4 +80° C. or higher.
- Example 19 in which MgO+CaO+SrO+BaO is more than 20% and MgO+Al 2 O 3 is less than 24%, has a high average thermal expansion coefficient ⁇ of 39 ⁇ 10 ⁇ 7 /K or more at 0 to 350° C., and a low specific elastic modulus of 36 MN ⁇ was less than m/kg.
- Example 20 with a B 2 O 3 content of less than 0.3% had a low Young's modulus E of less than 90 GPa and a low specific modulus of less than 36 MN ⁇ m/kg.
- Example 23 in which MgO + CaO + SrO + BaO is more than 20%, MgO/CaO is less than 1, MgO/(MgO + CaO + SrO + BaO) is less than 0.5, and MgO + Al 2 O 3 is less than 24% has a high average thermal expansion coefficient ⁇ at 0 to 350 ° C. It was greater than 39 ⁇ 10 ⁇ 7 /K.
- the alkali-free glass of the present embodiment can be used for display panels, semiconductor devices, carrier substrates for manufacturing flexible devices, carrier substrates for manufacturing semiconductor devices, information recording media, flat antennas, light control laminates, window glass for vehicles, acoustic It is preferable to use it for a vibration plate for a camera.
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Abstract
Description
(2)薄膜形成工程でガラス板が高温にさらされる際に、ガラス板の変形およびガラスの構造安定化に伴う収縮(熱収縮)を最小限に抑えうるように歪点が高いこと。
(4)内部および表面に欠点(泡、脈理、インクルージョン、ピット、キズ等)がないこと。
(5)ディスプレイの軽量化が要求され、ガラス自身も比重の小さいガラスが望まれる。
(6)ディスプレイの軽量化が要求され、ガラス板の薄板化が望まれる。
(7)これまでのアモルファスシリコン(a-Si)タイプの液晶ディスプレイに加え、熱処理温度の高い多結晶シリコン(p-Si)タイプの液晶ディスプレイが作製されるようになってきた(a-Siの耐熱性:約350℃、p-Siの耐熱性:350~550℃)ため、耐熱性が望まれる。
(9)また、近年、ガラス板の大板化・薄板化に伴い、比弾性率(ヤング率/密度)が高いガラスが求められている。
しかし、高ヤング率となるガラスは歪点が高く、ガラス粘度104dPa・sとなる温度T4に比べて失透温度が高くなる傾向にある。その結果、ガラス板への成形が難しくなる。
加えて、ガラス製造プロセスにおける要請から、ガラスの粘性、特にガラス粘度102dPa・sとなる温度T2およびガラス粘度104dPa・sとなる温度T4を低くすること、ガラス表面失透温度を低くすること、さらに、歪点を過度に上げ過ぎないことが求められている。
特許文献1、2に記載のガラスは、ヤング率が低く、比弾性率も低いため自重たわみを十分に小さくできない、もしくはヤング率が高く、さらに比弾性率も高くとも、平均熱膨張係数が高いため、耐熱衝撃性が低く、これらの要求を満たすことが難しかった。
酸化物基準のモル%表示で
SiO2 55%以上80%以下、
Al2O3 12%以上20%以下、
B2O3 0.3%以上5%以下、
MgO 5%以上18%以下、
CaO 0.1%以上12%以下、
SrO 0.1%以上8%以下、
BaO 0%以上6%以下
を含有し、
MgO+CaO+SrO+BaOが20%以下、
MgO/CaOが1以上、
MgO/(MgO+CaO+SrO+BaO)が0.5以上、
MgO+Al2O3が24%以上38%以下、
式(I)を(-3.125×[SiO2]-2.394×[Al2O3]-3.511×[B2O3]-2.167×[MgO]-2.608×[CaO]-3.161×[SrO]-3.583×[BaO]+3.795×102)としたとき、式(I)の値が90以上100以下である、無アルカリガラス。
[2] 式(II)を(0.213×[SiO2]+1.006×[Al2O3]-0.493×[B2O3]+1.158×[MgO]+1.386×[CaO]+3.092×[SrO]+4.198×[BaO]+2.004×102)としたとき、式(I)/式(II)×100の値が36以上である、[1]に記載の無アルカリガラス。
[3] (MgO+CaO)/(SrO+BaO)が8以上である、[1]または[2]に記載の無アルカリガラス。
[4] 50~350℃における平均線膨張係数をα、ヤング率をE、光弾性定数をCとしたとき、これらの積α・E・Cが9.2×10-7/K以下である、[1]~[3]のいずれかに記載の無アルカリガラス。
[5] 光弾性定数が31nm/MPa/cm以下である、[1]~[4]のいずれかに記載の無アルカリガラス。
[6] ガラス転移点が730℃以上850℃以下である、[1]~[5]のいずれかに記載の無アルカリガラス。
[7] ガラス表面失透粘度が103.4dPa・s以上である、[1]~[6]のいずれかに記載の無アルカリガラス。
[8] 酸化物基準のモル%表示で、ZrO2を0~1%含有する、[1]~[7]のいずれかに記載の無アルカリガラス。
[9] Li2O、Na2OおよびK2Oの合量が酸化物基準のモル%表示で0.2%以下である、[1]~[8]のいずれかに記載の無アルカリガラス。
[10] 酸化物基準のモル%表示で、SnO2を0%以上0.5%以下含有する、[1]~[9]のいずれかに記載の無アルカリガラス。
[11] モル%表示で、Fを0%以上1%以下含有する、[1]~[10]のいずれかに記載の無アルカリガラス。
[12] ガラスのβ-OH値が0.05mm-1以上0.6mm-1以下である、[1]~[11]のいずれかに記載の無アルカリガラス。
[13] [1]~[12]のいずれかに記載の無アルカリガラスを含むガラス板であり、少なくとも一辺が2400mm以上、厚みが1mm以下であるガラス板。
[14] [1]~[12]のいずれかに記載の無アルカリガラスの製造方法であって、フロート法又はフュージョン法で成形を行う、無アルカリガラスの製造方法。
以下において、ガラスの各成分の組成範囲は、酸化物基準のモル%で表示する。
SiO2の含有量が55モル%(以下、単に、%という)未満では、歪点が十分に上がらず、かつ、平均熱膨張係数が増大し、密度が上昇する傾向がある。そのため、SiO2の含有量は55%以上であり、好ましくは58%以上、より好ましくは60%以上、さらに好ましくは61%以上、特に好ましくは62%以上、最も好ましくは63%以上である。
SiO2の含有量が80%超では、ガラスの溶解性が低下し、ヤング率が低下し、ガラス表面失透温度(Tc)が上昇する傾向がある。そのため、SiO2の含有量は80%以下であり、好ましくは75%以下、より好ましくは73%以下、さらに好ましくは70%以下、特に好ましくは69%以下、最も好ましくは68%以下である。
Al2O3の含有量が12%未満では、これらの効果があらわれにくく、また、平均熱膨張係数を増大させる他成分が相対的に増加することになるため、結果的に平均熱膨張係数が大きくなる傾向がある。そのため、Al2O3の含有量は12%以上であり、好ましくは12.3%以上、より好ましくは12.6%以上、さらに好ましくは13%以上、なおさらに好ましくは13.3%以上、特に好ましくは13.6%以上、最も好ましくは14%以上である。
Al2O3の含有量が20%超ではガラスの溶解性が悪くなる、歪点を上昇させる、ガラス表面失透温度(Tc)を上昇させるおそれがある。そのため、Al2O3の含有量が20%以下であり、好ましくは18%以下、より好ましくは17.5%以下、さらに好ましくは17%以下、なおさらに好ましくは16.5%以下、特に好ましくは16%以下である、最も好ましくは15.5%以下である。
B2O3の含有量が0.3%未満では、これらの効果が現れにくい。そのため、B2O3の含有量は0.3%以上であり、好ましくは0.5%以上、より好ましくは0.6%以上、さらに好ましくは0.7%以上、特に好ましくは0.8%以上、最も好ましくは0.9%以上である。
MgOの含有量が5%未満では、これらの効果が現れにくく、また、熱膨張係数が低くなりすぎるおそれがある。そのため、MgOの含有量は5%以上である。MgOの含有量は、好ましくは7%以上、より好ましくは9%以上、さらに好ましくは10%以上、特に好ましくは10.5%以上、最も好ましくは11%以上である。
しかし、MgO含有量が多すぎると、ガラス表面失透温度(Tc)が上昇しやすくなる。そのため、MgOの含有量は18%以下であり、好ましくは17.5%以下、より好ましくは17%以下、さらに好ましくは16.5%以下、特に好ましくは16.3%以下、最も好ましくは16%以下である。
CaOの含有量が12%超では平均熱膨張係数が高くなりすぎ、またガラス表面失透温度(Tc)が高くなってガラスの製造時に失透が問題となりやすくなる。そのため、CaOの含有量は12%以下であり、好ましくは10%以下、より好ましくは9%以下、さらに好ましくは8.5%以下、特に好ましくは8%以下、最も好ましくは7.5%以下である。
SrOは上記効果がBaOよりも低く、SrO含有量が8%超では、SrOを多くしすぎるとむしろ密度を大きくする効果が勝り、平均熱膨張係数も高くなりすぎる。そのため、SrOの含有量は8%以下であり、好ましくは6%以下、より好ましくは5%以下、さらに好ましくは4%以下、特に好ましくは3%以下、最も好ましくは2%以下である。
BaOは多く含有すると密度が大きくなり、ヤング率が下がり、平均熱膨張係数が大きくなりすぎる傾向がある。そのため、BaOの含有量は6%以下であり、好ましくは5.5%以下、より好ましくは5%以下、特に好ましくは4.5%以下、最も好ましくは4%以下である。
なお、Baの毒性を考慮した場合は、BaOは実質的に含有しないことが好ましい。実質的に含有しないとは、不可避的不純物を除き含有しない意味であり、本実施形態においては、BaOの含有量は、例えば、0.1%未満であり、好ましくは0.05%以下、より好ましくは0.01%以下である。
ガラス表面失透温度(Tc)が低いと、ガラス表面失透粘度が高くなり、成形性が向上する。ガラス表面失透温度(Tc)を低くするには、MgO+CaO+SrO+BaOは好ましくは10%以上、より好ましくは12%以上、さらに好ましくは13%以上、なおさらに好ましくは14%以上、特に好ましくは15%以上、最も好ましくは16%以上である。ここで、MgO+CaO+SrO+BaOは、例えば、10%以上20%以下である。
一方、MgO/CaOが多すぎるとMgO-Al2O3-SiO2系の失透が出やすくなり、ガラス表面失透温度が高くなり、ガラス表面失透粘度が低くなる。そのため、MgO/CaOは好ましくは100以下、より好ましくは30以下、さらに好ましくは15以下、特に好ましくは10以下、最も好ましくは5以下である。ここで、MgO/CaOは、例えば、1以上100以下である。
一方、MgO-Al2O3-SiO2系の失透が出ることを抑え、失透温度の上昇を抑制するには、MgO/(MgO+CaO+SrO+BaO)は好ましくは0.95以下、より好ましくは0.9以下、さらに好ましくは0.85以下、特に好ましくは0.8以下である。ここで、MgO/(MgO+CaO+SrO+BaO)は、例えば、0.5以上0.95以下である。
MgO+Al2O3が24%未満だと、ヤング率が低くなり、外部応力に対する基板の変形が大きくなる。そのため、MgO+Al2O3は24%以上とする。MgO+Al2O3は、好ましくは24.2%以上、より好ましくは24.5%以上、さらに好ましくは25%以上、特に好ましくは25.5%以上、最も好ましくは26%以上である。
一方、MgO+Al2O3が38%超だと、失透温度が上昇し、成形性が悪化する。そのため、MgO+Al2O3は38%以下とする。MgO+Al2O3は好ましくは35%以下、より好ましくは33%以下、さらに好ましくは32%以下、特に好ましくは31%以下、最も好ましくは30%以下である。
一方、(MgO+CaO)/(SrO+BaO)が200以下であると、失透温度の上昇を抑制できるため好ましい。(MgO+CaO)/(SrO+BaO)は好ましくは100以下、より好ましくは75以下、さらに好ましくは60以下、特に好ましくは50以下である。ここで、(MgO+CaO)/(SrO+BaO)は、例えば、8以上200以下である。
式(I)で表される値はヤング率の指標であり、この値が90未満であると、ヤング率が低くなりやすく、比弾性率が小さくなりやすく、自重たわみが大きくなりやすい。100超であると、ヤング率が大きくなりすぎて、切断マージンが損なわれる。式(I)で表される値は、好ましくは90.5以上97以下、より好ましくは90.8以上95以下、さらに好ましくは91以上94以下、特に好ましくは91.2以上93.5以下、最も好ましくは91.5以上93以下である。
なお、式における[金属酸化物]との記載(例えば[SiO2])は、当該の金属酸化物成分をモル%で表記した時の数値を表す(本明細書の他の部分の記載において同じ。)。例えば、酸化物基準のモル%の表示で、SiO2が60モル%であった場合、[SiO2]は60を表す。
式(I)/式(II)×100で表される値は比弾性率の指標である。式(I)/式(II)×100で表される値が、36以上であると、比弾性率が高くなるため好ましい。式(I)/式(II)×100の値は、より好ましくは36.1以上、さらに好ましくは36.2以上、なおさらに好ましくは36.3以上、特に好ましくは36.4以上、最も好ましくは36.5以上である。
式(I)/式(II)×100の値が、50以下であると切断マージンを維持できるため好ましい。ここで、式(I)/式(II)×100の値は、例えば、36以上50以下である。
式(II)で表される値はより好ましくは242以上259以下、さらに好ましくは244以上258以下、なおさらに好ましくは246以上257以下、特に好ましくは248以上256以下、最も好ましくは250以上255以下である。
但し、ZrO2の含有量が多すぎると、ガラス表面失透温度が高くなるおそれがあり、誘電率εが高くなるおそれがあり、ガラスが不均一になるおそれがある。また、半導体デバイスに適用した場合、α線による故障を生じさせるおそれがある。そのため、ZrO2の含有量は1%以下が好ましく、より好ましくは0.5%以下、さらに好ましくは0.2%以下、なおさらに好ましくは0.1%以下、ことさらに好ましくは0.05%以下、よりいっそう好ましくは0.04%以下、特に好ましくは0.03%以下、実質的に含有しないことが最も好ましい。ZrO2を実質的に含有しないとは、原料等から混入する不可避的不純物以外には含有しないこと、すなわち、意図的に含有させないことを意味する。本実施形態において、ZrO2を実質的に含有しないとは、ZrO2の含有量が、例えば0.01%以下、好ましくは0.005%以下である。
ガラスの溶解性を向上させたい場合には、Fe含有量がFe2O3換算で0.002%以上がより好ましく、0.005%以上がさらに好ましく、0.008%以上がなおさらに好ましく、0.01%以上がことさらに好ましく、0.02%以上がよりいっそう好ましく、0.03%以上が特に好ましく、0.04%以上が最も好ましい。
Cl含有量が1.0%以下だと、ガラス製造時に泡層の肥大化を抑制する作用が良好である。好ましくは0.8%以下、より好ましくは0.6%以下である。
β-OH値は、ガラス中の水分含有量の指標であり、ガラス試料について波長2.75~2.95μmの光に対する吸光度を測定し、吸光度の最大値βmaxを該試料の厚さ(mm)で割ることで求める。ガラスのβ-OH値は0.45mm-1以下がより好ましく、さらに好ましくは0.4mm-1以下、なおさらに好ましくは0.35mm-1以下、ことさらに好ましくは0.3mm-1以下、よりいっそう好ましくは0.28mm-1以下、特に好ましくは0.25mm-1以下、最も好ましくは0.23mm-1以下である。一方、β-OH値が0.05mm-1以上であると、後述するガラスの歪点を達成しやすい。そのため、β-OH値は0.08mm-1以上がより好ましく、さらに好ましくは0.1mm-1以上、なおさらに好ましくは0.13mm-1以上であり、ことさらに好ましくは0.15mm-1以上、特に好ましくは0.18mm-1以上、最も好ましくは0.2mm-1以上である。
一方、歪点が高すぎると、それに応じて徐冷装置の温度を高くする必要があり、徐冷装置の寿命が低下する傾向がある。そのため、740℃以下である。歪点は好ましくは738℃以下、より好ましくは736℃以下、さらに好ましくは735℃以下である。
一方、密度が2.4g/cm3以上であると、搬送時の安定性が良好になるため好ましい。密度はより好ましくは2.42g/cm3以上、さらに好ましくは2.44g/cm3以上、なおさらに好ましくは2.46g/cm3以上、特に好ましくは2.48g/cm3以上、最も好ましくは2.5g/cm3以上である。ここで、密度は例えば、2.4g/cm3以上2.6g/cm3以下である。
ヤング率が100GPa以下であると、切断マージンが大きくなる。ヤング率は好ましくは98GPa以下、より好ましくは97GPa以下、さらに好ましくは96GPa以下、最も好ましくは95GPa以下である。ヤング率は超音波法により測定できる。
50~350℃での平均熱膨張係数は好ましくは30.5×10-7/K以上、より好ましくは31×10-7/K以上、さらに好ましくは31.5×10-7/K以上、特に好ましくは32×10-7/K以上、最も好ましくは32.5×10-7/K以上である。
一方、50~350℃での平均熱膨張係数が39×10-7/K超だと、ディスプレイなどの製品製造工程でガラスが割れるおそれがあり、また、ガラスの耐熱衝撃性が低くなる。そのため、39×10-7/K以下である。
50~350℃での平均熱膨張係数は好ましくは38.5×10-7/K以下、より好ましくは38×10-7/K以下、さらに好ましくは37.5×10-7/K以下、特に好ましくは37.3×10-7/K以下、最も好ましくは37×10-7/K以下である。ここで、50~350℃での平均熱膨張係数は、例えば、30×10-7/K以上39×10-7/K以下である。
一方、T2が1690℃以下であると、ガラスの溶解性に優れる。そのため、製造設備への負担を低くできる。例えば、ガラスを溶解する窯など設備寿命を延ばすことができ、生産性を向上できる。また、窯由来の欠陥(例えば、ブツ欠陥、Zr欠陥など)を低減できる。T2は好ましくは1670℃以下、より好ましくは1660℃以下、さらに好ましくは1650℃以下、なおさらに好ましくは1640℃以下、最も好ましくは1635℃以下である。
T4の下限は特に限定されないが、通常1100℃以上である。T4は例えば、1100℃以上1350℃以下である。
T2、T4はASTM C 965-96に規定されている方法に従い、回転粘度計を用いて粘度を測定し、102d・Pa・sとなるときの温度をT2、104d・Pa・sとなるときの温度をT4として求めることができる。なお、後述する実施例では、装置校正用の参照試料としてNBS710およびNIST717aを使用した。
Tcは、好ましくはT4+75℃以下、より好ましくはT4+70℃以下、さらに好ましくはT4+60℃以下、なおさらに好ましくはT4+50℃以下、特に好ましくはT4+40℃以下、最も好ましくはT4+30℃以下である。
Tcの下限は特に限定されないが、通常1000℃以上である。Tcは例えば、1000℃以上T4+80℃未満である。
本実施形態におけるガラス表面失透温度(Tc)は、下記のように求めることができる。すなわち、白金製の皿に粉砕されたガラス粒子を入れ、一定温度に制御された電気炉中で17時間熱処理を行い、熱処理後に光学顕微鏡を用いて、ガラスの表面に結晶が析出する最高温度と結晶が析出しない最低温度とを観察し、その平均値をガラス表面失透温度(Tc)とする。
ηcの上限は特に限定されないが、通常106dPa・s以下である。ηcは例えば、103.4dPa・s以上106dPa・s以下である。
比弾性率の上限は特に限定されないが、通常50MN・m/kg以下である。比弾性率は、例えば、36MN・m/kg以上50MN・m/kg以下である。
なお、大型基板とは、例えば、少なくとも一辺が1800mm以上の基板である。大型基板の少なくとも一辺は、例えば、2000mm以上であってもよく、2500mm以上であってもよく、3000mm以上であってもよく、3500mm以上であってもよい。
液晶ディスプレイパネル製造工程や液晶ディスプレイ装置使用時に発生した応力により、ガラス基板が複屈折性を有し、黒の表示がグレーになり、液晶ディスプレイのコントラストが低下することがある。光弾性定数を31nm/MPa/cm以下であれば、この現象を抑制できる。光弾性定数はより好ましくは30nm/MPa/cm以下、さらに好ましくは29nm/MPa/cm以下、なおさらに好ましくは28nm/MPa/cm以下、特に好ましくは27.5nm/MPa/cm以下、最も好ましくは27nm/MPa/cm以下である。
他の物性確保の容易性を考慮すると、光弾性定数は、光弾性定数が23nm/MPa/cm以上が好ましく、より好ましくは25nm/MPa/cm以上である。なお、光弾性定数は円板圧縮法により測定波長546nmにて測定できる。ここで、光弾性定数は23nm/MPa/cm以上31nm/MPa/cm以下であることが好ましい。
液晶ディスプレイでは、バックライトからの熱により、バックライトに近い側のガラス板(TFT-LCDにおいてはアレイ用ガラス板)の温度分布が不均一となる。ガラス板内の最高温度と最低温度の差をΔTとすると、このガラス板内に発生する応力の最大値Fは次式によって表される。
F=α・E・ΔT
この応力Fによって厚さのガラス板に発生する光路差すなわちリターデーションRは次式によって表される。
R=C・F・L=(α・E・C)・ΔT・L
そのため、α・E・Cが小さいほどRは小さくなり、液晶ディスプレイのコントラストが良好になる。
α・E・Cが9.2×10-7/K以下であると、本実施形態の無アルカリガラスを液晶ディスプレイ用のガラス板として使用した場合に、液晶ディスプレイのコントラストが良好にあり、コントラスト不良が起こりにくくなる。
α・E・Cの下限は特に限定されないが、通常5×10-7/K以上である。α・E・Cは、5×10-7/K以上9.2×10-7/K以下であることが好ましい。
上記各成分の原料をガラス組成中で目標含有量となるように調合し、これを溶解炉に投入し、1500~1800℃に加熱して溶解して溶融ガラスを得る。得られた溶融ガラスを成形装置にて、所定の板厚のガラスリボンに成形し、このガラスリボンを徐冷後、切断することによって無アルカリガラスが得られる。
ガラス組成が例1~55に示す目標組成(単位:モル%)になるように、各成分の原料を調合し、白金坩堝を用いて1600℃で1時間溶解した。溶解後、溶融液をカーボン板上に流し出し、(ガラス転移点+30℃)の温度にて60分保持後、毎分1℃で室温(25℃)まで冷却して板状ガラスを得た。これを鏡面研磨し、ガラス板を得て、各種評価を行った。なお、ガラスのβ-OH値は以下の手順で求めた。
(β-OH値)
ガラス試料について波長2.75~2.95μmの光に対する吸光度を測定し、吸光度の最大値βmaxを該試料の厚さ(mm)で割ることでβ-OH値を求めた。
結果を表1~表8に示す。なお、表1~表8において、括弧内に示す値は計算値である。
(平均熱膨張係数α)
JIS R3102(1995年)に規定されている方法に従い、示差熱膨張計(ディラトメーター)を用いて測定した。測定温度範囲は室温~400℃以上とし、50~350℃における平均熱膨張係数を、単位を10-7/Kとして表した。
(密度)
JIS Z 8807に規定されている方法に従い、泡を含まない約20gのガラス塊をアルキメデス法によって測定した。
(歪点)
JIS R3103-2(2001年)に規定されている方法に従い、繊維引き伸ばし法により測定した。
(Tg)
JIS R3103-3(2001年)に規定されている方法に従い、熱膨張法により測定した。
(ヤング率)
JIS Z 2280に規定されている方法に従い、厚さ0.5~10mmのガラスについて、超音波パルス法により測定した。
ASTM C 965-96に規定されている方法に従い、回転粘度計を用いて粘度を測定し、102d・Pa・sとなるときの温度T2(℃)を測定した。
(T4)
ASTM C 965-96に規定されている方法に従い、回転粘度計を用いて粘度を測定し、104d・Pa・sとなるときの温度T4(℃)を測定した。
(ガラス表面失透温度Tc)
ガラスを粉砕し、試験用篩を用いて粒径が2~4mmの範囲となるように分級した。得られたガラスカレットをイソプロピルアルコール中で超音波洗浄を5分間行い、イオン交換水で洗浄した後、乾燥させ、白金製の皿に入れ、一定温度に制御された電気炉中で17時間の熱処理を行った。熱処理の温度は10℃間隔で設定した。
熱処理後、白金皿よりガラスを取り外し、光学顕微鏡を用いて、ガラスの表面に結晶が析出する最高温度と結晶が析出しない最低温度とを観察した。
ガラスの表面に結晶が析出する最高温度と結晶が析出しない最低温度は、それぞれ1回測定した。(結晶析出の判断が難しい場合、2回測定した。)
ガラス表面に結晶が析出する最高温度と結晶が析出しない最低温度との測定値を用いて平均値を求め、ガラス表面失透温度Tcとした。
なお、下記表では、請求項1で規定するTcがT4+80℃未満との関係を判別しやすくするため、Tc-T4で示した。
(ガラス表面失透粘度ηc)
前述の方法により、ガラス表面失透温度(Tc)を求め、ガラス表面失透温度(Tc)におけるガラスの粘度を測定して、ガラス表面失透粘度(ηc)を求めた。なお、下記表では、ガラス表面失透粘度(ηc)の対数値(log値)を示した。
(比弾性率)
前述した手順で求まるヤング率を密度で割ることにより、比弾性率を求めた。
光弾性定数は円板圧縮法により測定波長546nmにて測定した。
(BHFヘイズ)
ガラス板を25℃の19BHF溶液に20分間浸漬した前後のヘイズ変化が1%以下であれば○、1%超のときは×とした。
MgO/(MgO+CaO+SrO+BaO)が0.5未満、MgO+Al2O3が24%未満、式(I)の値が90未満の例16は、50~350℃での平均熱膨張係数αが高く39×10-7/K超であり、ヤング率Eが低く90GPa未満であり、比弾性率が低く36MN・m/kg未満であった。
B2O3およびSrOを含まず、MgO+CaO+SrO+BaOが20%超の例17は、歪点が高く740℃超であり、ガラス粘度102dPa・sとなる温度T2が低く1590℃未満であった。
B2O3およびSrOを含まず、Al2O3含有量が12%未満、MgO+CaO+SrO+BaOが20%超の例18は、ガラス表面失透温度(Tc)がT4+80℃以上であった。
MgO+CaO+SrO+BaOが20%超、MgO+Al2O3が24%未満の例19は、0~350℃での平均熱膨張係数αが高く39×10-7/K超であり、比弾性率が低く36MN・m/kg未満であった。
B2O3含有量が0.3%未満の例20は、ヤング率Eが低く90GPa未満であり、比弾性率が低く36MN・m/kg未満であった。
MgO+CaO+SrO+BaOが20%超の例21は、0~350℃での平均熱膨張係数αが高く39×10-7/K超であり、ガラス粘度102dPa・sとなる温度T2が低く1590℃未満であった。
MgO+CaO+SrO+BaOが20%超の例22は、密度が高く2.6g/cm3超であり、ヤング率Eが低く90GPa未満であった。
MgO+CaO+SrO+BaOが20%超、MgO/CaOが1未満、MgO/(MgO+CaO+SrO+BaO)が0.5未満、MgO+Al2O3が24%未満の例23は、0~350℃での平均熱膨張係数αが高く39×10-7/K超であった。
Claims (14)
- 歪点が700℃以上740℃以下、密度が2.6g/cm3以下、ヤング率が90GPa以上100GPa以下、50~350℃での平均熱膨張係数が30×10-7/K以上39×10-7/K以下、ガラス粘度102dPa・sとなる温度T2が1590℃以上1690℃以下、ガラス粘度104dPa・sとなる温度T4が1350℃以下、ガラス表面失透温度(Tc)がT4+80℃未満、比弾性率が36MN・m/kg以上であり、
酸化物基準のモル%表示で
SiO2 55%以上80%以下、
Al2O3 12%以上20%以下、
B2O3 0.3%以上5%以下、
MgO 5%以上18%以下、
CaO 0.1%以上12%以下、
SrO 0.1%以上8%以下、
BaO 0%以上6%以下
を含有し、
MgO+CaO+SrO+BaOが20%以下、
MgO/CaOが1以上、
MgO/(MgO+CaO+SrO+BaO)が0.5以上、
MgO+Al2O3が24%以上38%以下、
式(I)を(-3.125×[SiO2]-2.394×[Al2O3]-3.511×[B2O3]-2.167×[MgO]-2.608×[CaO]-3.161×[SrO]-3.583×[BaO]+3.795×102)としたとき、式(I)の値が90以上100以下である、無アルカリガラス。 - 式(II)を(0.213×[SiO2]+1.006×[Al2O3]-0.493×[B2O3]+1.158×[MgO]+1.386×[CaO]+3.092×[SrO]+4.198×[BaO]+2.004×102)としたとき、式(I)/式(II)×100の値が36以上である、請求項1に記載の無アルカリガラス。
- (MgO+CaO)/(SrO+BaO)が8以上である、請求項1または2に記載の無アルカリガラス。
- 50~350℃における平均線膨張係数をα、ヤング率をE、光弾性定数をCとしたとき、これらの積α・E・Cが9.2×10-7/K以下である、請求項1~3のいずれかに記載の無アルカリガラス。
- 光弾性定数が31nm/MPa/cm以下である、請求項1~4のいずれかに記載の無アルカリガラス。
- ガラス転移点が730℃以上850℃以下である、請求項1~5のいずれかに記載の無アルカリガラス。
- ガラス表面失透粘度が103.4dPa・s以上である、請求項1~6のいずれかに記載の無アルカリガラス。
- 酸化物基準のモル%表示で、ZrO2を0~1%含有する、請求項1~7のいずれかに記載の無アルカリガラス。
- Li2O、Na2OおよびK2Oの合量が酸化物基準のモル%表示で0.2%以下である、請求項1~8のいずれかに記載の無アルカリガラス。
- 酸化物基準のモル%表示で、SnO2を0%以上0.5%以下含有する、請求項1~9のいずれかに記載の無アルカリガラス。
- モル%表示で、Fを0%以上1%以下含有する、請求項1~10のいずれかに記載の無アルカリガラス。
- ガラスのβ-OH値が0.05mm-1以上0.6mm-1以下である、請求項1~11のいずれかに記載の無アルカリガラス。
- 請求項1~12のいずれかに記載の無アルカリガラスを含むガラス板であり、少なくとも一辺が2400mm以上、厚みが1mm以下であるガラス板。
- 請求項1~12のいずれかに記載の無アルカリガラスの製造方法であって、フロート法又はフュージョン法で成形を行う、無アルカリガラスの製造方法。
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JP (1) | JPWO2023037951A1 (ja) |
KR (1) | KR20240052945A (ja) |
CN (1) | CN117916207A (ja) |
TW (1) | TW202325673A (ja) |
WO (1) | WO2023037951A1 (ja) |
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JP2011105554A (ja) * | 2009-11-19 | 2011-06-02 | Nippon Electric Glass Co Ltd | ガラス繊維用ガラス組成物、ガラス繊維及びガラス製シート状物 |
WO2013183625A1 (ja) * | 2012-06-05 | 2013-12-12 | 旭硝子株式会社 | 無アルカリガラスおよびその製造方法 |
WO2019082590A1 (ja) * | 2017-10-25 | 2019-05-02 | 日本板硝子株式会社 | ガラス組成物 |
JP2019194156A (ja) * | 2014-10-23 | 2019-11-07 | Agc株式会社 | 無アルカリガラス |
CN111302619A (zh) * | 2020-04-17 | 2020-06-19 | 中南大学 | 一种无碱铝硼硅酸盐玻璃及其制备方法 |
CN111747645A (zh) * | 2020-06-05 | 2020-10-09 | 蚌埠中光电科技有限公司 | 一种铝硅酸盐玻璃 |
Family Cites Families (1)
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CN111836791B (zh) | 2018-03-14 | 2023-01-17 | Agc株式会社 | 无碱玻璃 |
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- 2022-08-31 JP JP2023546909A patent/JPWO2023037951A1/ja active Pending
- 2022-08-31 WO PCT/JP2022/032891 patent/WO2023037951A1/ja active Application Filing
- 2022-08-31 CN CN202280060280.8A patent/CN117916207A/zh active Pending
- 2022-09-05 TW TW111133505A patent/TW202325673A/zh unknown
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2024
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Patent Citations (6)
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JP2011105554A (ja) * | 2009-11-19 | 2011-06-02 | Nippon Electric Glass Co Ltd | ガラス繊維用ガラス組成物、ガラス繊維及びガラス製シート状物 |
WO2013183625A1 (ja) * | 2012-06-05 | 2013-12-12 | 旭硝子株式会社 | 無アルカリガラスおよびその製造方法 |
JP2019194156A (ja) * | 2014-10-23 | 2019-11-07 | Agc株式会社 | 無アルカリガラス |
WO2019082590A1 (ja) * | 2017-10-25 | 2019-05-02 | 日本板硝子株式会社 | ガラス組成物 |
CN111302619A (zh) * | 2020-04-17 | 2020-06-19 | 中南大学 | 一种无碱铝硼硅酸盐玻璃及其制备方法 |
CN111747645A (zh) * | 2020-06-05 | 2020-10-09 | 蚌埠中光电科技有限公司 | 一种铝硅酸盐玻璃 |
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CN117916207A (zh) | 2024-04-19 |
TW202325673A (zh) | 2023-07-01 |
KR20240052945A (ko) | 2024-04-23 |
US20240199469A1 (en) | 2024-06-20 |
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