CN114590996A - Optical glass, preform, and optical element - Google Patents
Optical glass, preform, and optical element Download PDFInfo
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- CN114590996A CN114590996A CN202210322226.8A CN202210322226A CN114590996A CN 114590996 A CN114590996 A CN 114590996A CN 202210322226 A CN202210322226 A CN 202210322226A CN 114590996 A CN114590996 A CN 114590996A
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- optical glass
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- 239000005304 optical glass Substances 0.000 title claims abstract description 70
- 230000003287 optical effect Effects 0.000 title claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000011521 glass Substances 0.000 claims description 96
- 239000000203 mixture Substances 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 7
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 7
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 7
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 7
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 7
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910003069 TeO2 Inorganic materials 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 6
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000000956 alloy Substances 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 38
- 238000004031 devitrification Methods 0.000 description 28
- 238000005299 abrasion Methods 0.000 description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 19
- 238000002834 transmittance Methods 0.000 description 18
- 238000002156 mixing Methods 0.000 description 14
- 238000005498 polishing Methods 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000006060 molten glass Substances 0.000 description 8
- 238000004040 coloring Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012768 molten material Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910020440 K2SiF6 Inorganic materials 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 2
- 229910004883 Na2SiF6 Inorganic materials 0.000 description 2
- 229910007998 ZrF4 Inorganic materials 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910000149 boron phosphate Inorganic materials 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910005693 GdF3 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002339 La(NO3)3 Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical class OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Inorganic materials [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
-
- 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
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
-
- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
-
- 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
- C03C4/00—Compositions for glass with special properties
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides an optical glass, a preform and an optical element, wherein the optical glass contains P by mass percent2O535.0% to 65.0% of component B2O3More than 0% to 20.0% inclusive, more than 0% to 30.0% inclusive of BaO, and more than 0% to 35.0% inclusive of SrO; mass ratio (B)2O3SrO is greater than 0, has a refractive index (n)d)1.55 to 1.70 of the total weight of the alloy,abbe number (v)d)45 to 75, and chemical durability (acid resistance) according to the powder method is grade 1 to grade 5. By means of the invention, the refractive index (n) can be obtainedd) And Abbe number (. nu.)d) All of which are within a desired range and have high acid resistance according to the powder method.
Description
Technical Field
The invention relates to an optical glass, a preformed body and an optical element.
Background
In recent years, digitalization and high definition of devices using optical systems have been rapidly advancing, and in the field of various optical devices such as video cameras such as digital cameras and video cameras, and image reproducing (projection) devices such as projectors and projection televisions, there is an increasing demand for a glass material that is easy to process in order to improve process yield and suppress cost.
In the optical glass for producing an optical element, particularly for a glass having a refractive index (n) of 1.55 to 1.70d) And a low Abbe number (v) of 45 to 75d) And the demand for improving the processability of the fluorine-free phosphoric acid glass is very high. As such a fluorine-free phosphoric acid glass, a glass composition as represented in patent document 1 is known.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2012 and 51781.
Disclosure of Invention
Technical problem to be solved by the invention
In order to apply the optical glass to various optical machines, polishing, cleaning, or the like is required. The use of an abrasive material in the polishing step or a cleaning agent in the cleaning step tends to cause flaws in the glass which are inferior in chemical durability, particularly acid resistance. Further, since it is difficult to handle glass having a high degree of abrasion when it is processed, it is desirable to use glass having a low degree of abrasion as much as possible. However, it is difficult to say that the glass described in patent document 1 sufficiently satisfies such a demand.
In view of the above problems, the present invention is to provide a refractive index (n)d) And Abbe number (v)d) An optical glass which is easy to be subjected to glass processing in a polishing step or a cleaning step and which is less likely to cause a flaw in the glass surface when each glass step is performed, is within a desired range.
Means for solving the problems
The inventors and the likeIn order to solve the above problems, the present inventors have focused on the results of cumulative experimental studies and found that P is the target of P2O5The component B is used as the main component2O3Component (B), SrO component, and BaO component2O3When the mass ratio of the component (a) to the SrO component is a predetermined amount, a glass having a desired high refractive index and high dispersion, good acid resistance according to the powder method, and a small abrasion degree can be obtained, and the present invention has been completed.
Specifically, the present invention provides the following.
(1) An optical glass comprising, in mass%, P2O535.0 to 65.0% of component B2O3A component of more than 0% and not more than 20.0%, a BaO component of more than 0% and not more than 30.0%, and a SrO component of more than 0% and not more than 35.0%; mass ratio (B)2O3SrO is greater than 0, has a refractive index (n)d)1.55 to 1.70, Abbe number (. nu.d)45 to 75, and chemical durability (acid resistance) according to the powder method is grade 1 to grade 5.
(2) The optical glass as described in (1), wherein SiO2The component is 0% to 10.0%, the component of MgO is 0% to 15.0%, the component of CaO is 0% to 15.0%, the component of ZnO is 0% to 25.0%, La2O3The component (A) is 0-15.0%, Gd2O3The component (B) is 0-15.0%, Y2O3The components are 0-15.0% and Yb2O3The component (B) is0 to 15.0%, ZrO2The component (B) is0 to 10.0%, Nb2O5The component (B) is0 to 10.0%, WO3The component (B) is0 to 10.0 percent, TiO2The component (B) is0 to 10.0%, Ta2O5The component (B) is0 to 5.0%, Li2O component is 0-10.0%, Na2O component is 0% to 10.0%, K2The O component is 0-10.0%, GeO2The component (A) is 0-10.0%, Al2O3Component (B) is0 to 10.0%, Ga2O3The component (B) is0 to 10.0 percent, Bi2O3The component (B) is 0-10.0%, TeO2The component (B) is0 to 10.0%, SnO2Component (C) is0% to 3.0%, Sb2O3The component (B) is0 to 1.0%, and the content of F as a fluoride obtained by partially or completely replacing 1 or 2 or more oxides of the above elements is0 to 10.0% by mass.
(3) The optical glass according to (1) or (2), wherein the sum of the contents of RO components (wherein R is1 or more selected from the group consisting of Mg, Ca, Sr, Ba) is 10.0% to 50.0% by mass, and Rn2The sum of the contents of O component (Rn is more than 1 selected from the group consisting of Li, Na and K) is less than 15.0%, Ln2O3The total amount of the components (Ln is1 or more selected from the group consisting of La, Gd, Y and Yb) is 20.0% or less.
(4) The optical glass as described in any one of (1) to (3), wherein the mass ratio (SrO/BaO) is more than 0 and less than 15.0.
(5) The optical glass as described in any one of (1) to (4), wherein the mass sum (BaO + Gd)2O3) Is more than 0% and less than 50.0%.
(6) A preform made of the optical glass as described in any one of (1) to (5).
(7) An optical element comprising the optical glass according to any one of (1) to (5).
(8) An optical device comprising the optical element according to (7).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a refractive index (n) thereof can be obtainedd) And Abbe number (v)d) All of which are within a desired range and have good chemical durability (acid resistance) according to the powder method.
Further, according to the present invention, it is possible to obtain not only the refractive index (n) thereofd) And Abbe number (v)d) All of which are within a desired range, and which have a low degree of abrasion and good workability.
Detailed Description
The optical glass of the present invention contains P in mass%2O535.0 to 65.0% of component B2O3The component is more than 0% and small20.0% or more, a BaO component of more than 0% and 30.0% or less, and a SrO component of more than 0% and 35.0% or less; mass ratio (B)2O3Has a refractive index (n) greater than 0d)1.55 to-1.70, Abbe number (v)d)45 to 75, and chemical durability (acid resistance) according to the powder method is grade 1 to grade 5. According to the invention, by containing P2O5Component (B)2O3Component (B), a BaO component and a SrO component as essential components, and the mass ratio of the components (B)2O3SrO) is adjusted to a predetermined amount, and optical glass having a desired refractive index and abbe number and excellent acid resistance can be obtained.
The optical glass of the present invention is described below in detail with reference to embodiments thereof, but the present invention is not limited to the embodiments below and can be carried out with appropriate modifications within the scope of the object of the present invention. Note that, although description of overlapping portions may be omitted as appropriate, the invention is not limited thereto.
[ glass composition ]
The composition ranges of the components constituting the optical glass of the present invention are as follows. In the present specification, the content of each component is expressed in mass% relative to the entire mass of the glass in terms of oxide composition unless otherwise specified. Here, the "composition in terms of oxides" refers to the composition of each component contained in the glass, assuming that all of the oxides, complex salts, metal fluorides, and the like used as raw materials of the glass composition component of the present invention are decomposed to oxides during melting, assuming that the total mass of the oxides is 100 mass%.
< essential Components, optional Components >
In the optical glass of the present invention, P2O5The component is an essential component and a main component for forming the glass, and is a component for improving the viscosity of the glass and improving the stability of the glass.
If P2O5When the content of the component is too small, the glass may become unstable and the viscosity may be lowered, or the stability of the glass may be deteriorated, becauseIn the optical glass of the present invention, P is2O5The content of component (c) is preferably 35.0% or more, more preferably 38.0% or more, and still more preferably 40.0% or more.
On the other hand, if P2O5If the content of the component (B) is too large, the refractive index decreases, and therefore P2O5The content of the component (b) is preferably 65.0% or less, more preferably 62.0% or less, still more preferably 60.0% or less, and further preferably 58.0% or less.
P2O5As the component (C), Al (PO) can be used3)3、Ca(PO3)2、Ba(PO3)2、BPO4、H3PO4And the like as a raw material.
B2O3The component (c) is an essential component which is essential for the optical glass of the present invention containing a plurality of rare earth oxides and is an oxide formed as a glass. In particular, the optical glass of the present invention can be obtained by containing more than 0% of B2O3Component (b) can improve the meltability of the glass. Thus, B2O3The content of the component (c) is preferably more than 0%, more preferably 1.0% or more, and still more preferably more than 2.0%.
On the other hand, by mixing B2O3The content of the component (B) is 20.0% or less, and deterioration of chemical durability can be suppressed. Thus, B2O3The content of the component (b) is preferably 18.0% or less, more preferably less than 15.0%, and still more preferably less than 13.0%.
B2O3Component (C) can be H3BO3、Na2B4O7、Na2B4O7·10H2O、BPO4And the like as a raw material.
The BaO component has the effect of increasing the refractive index of the glass and improving the stability of the glass, and is an essential component in the present invention. Therefore, the content of the BaO component is preferably more than 0%, more preferably more than 1.0%, still more preferably more than 1.5%.
On the other hand, if the content of the BaO component is too large, the acid resistance is deteriorated and the abrasion degree is increased, so that it is difficult to improve the processability which is the object of the optical glass of the present invention. Therefore, the content of the BaO component is preferably 30.0% or less, more preferably 25.0% or less, and still more preferably 20.0% or less.
BaO component, BaCO can be used3、Ba(NO3)2、Ba(PO3)2、BaF2And the like as a raw material.
The SrO component has an effect of reducing the degree of abrasion while maintaining a desired refractive index or dispersion, and is an essential component in the present invention. Therefore, the content of the SrO component is preferably more than 0%, more preferably more than 1.5%, and still more preferably more than 3.0%.
On the other hand, if the content of the SrO component is too large, acid resistance is deteriorated and the glass becomes unstable. Therefore, the content of the SrO component is preferably 35.0% or less, more preferably 30.0% or less, still more preferably 28.0% or less, still more preferably 26.0% or less, and still more preferably 25.0% or less.
SrO component, Sr (NO) may be used3)2、SrF2、Sr(PO3)2And the like as a raw material.
In order to obtain a glass having good abrasion, B2O3The ratio (mass ratio) of the content of the component to the content of the SrO component is preferably greater than 0. Therefore, mass ratio (B)2O3SrO) is preferably more than 0, more preferably 0.05 or more, still more preferably 0.11 or more.
On the other hand, by setting the mass ratio to less than 1.80, acid resistance can be improved, and therefore, the mass ratio (B)2O3SrO) is preferably less than 1.80, more preferably less than 1.70, still more preferably less than 1.50, further preferably less than 1.30, further preferably less than 1.15, still further preferably less than 1.11.
SiO2When the component (b) is an optional component and the content thereof is more than 0%, the viscosity of the molten glass can be increased, the coloring of the glass can be reduced, and the devitrification resistance can be improved.
On the other hand, by mixing SiO2Since the content of the component (A) is 10.0% or less, stable glass can be obtained, SiO2The content of the component (b) is preferably 10.0% or less, more preferably less than 5.0%, and still more preferably less than 3.0%.
SiO2Component (C), SiO can be used2、K2SiF6、Na2SiF6And the like as a raw material.
The MgO component is an arbitrary component, and when the content thereof is more than 0%, the reduction rate of acid resistance can be reduced and the degree of abrasion can be reduced.
On the other hand, by setting the content of the MgO component to 15.0% or less, the refractive index reduction or devitrification due to the excessive content of the component can be reduced. Therefore, the content of the MgO component is preferably 15.0% or less, more preferably less than 13.0%, and still more preferably less than 10.0%.
MgO component, MgCO can be used3、MgF2、MgO、4MgCO3·Mg(OH)2And the like as a raw material.
The CaO component is an optional component, and when the content thereof is more than 0%, the meltability of the glass raw material and the devitrification resistance of the glass can be improved.
On the other hand, by setting the content of the CaO component to 15.0% or less, it is possible to reduce the decrease in refractive index or devitrification due to the excessive content of the CaO component. The content of the CaO component is preferably 15.0% or less, more preferably less than 13.0%, and still more preferably less than 11.0%.
CaO component, CaCO may be used3、CaF2And the like as a raw material.
The ZnO component is an optional component, which can improve resistance to devitrification, and when the content thereof is more than 0%, the glass transition point can be lowered, the specific gravity can be reduced, and chemical durability can be improved. Therefore, the content of the ZnO component is preferably more than 0%, more preferably more than 0.5%, still more preferably more than 1.0%, and further preferably more than 2.0%.
On the other hand, by setting the content of the ZnO component to 25.0% or less, low dispersion can be maintained. Therefore, the content of the ZnO component is preferably 25.0% or less, more preferably 23.0% or less, and still more preferably 21.0% or less.
ZnO or ZnF can be used as the ZnO component2And the like as a raw material.
La2O3The component is an arbitrary component, and when the content thereof is more than 0%, the rate of decrease in acid resistance and the degree of abrasion can be reduced.
On the other hand, if the content is large, devitrification resistance is deteriorated, and therefore, La2O3The content of the component (b) is preferably 15.0% or less, more preferably less than 10.0%, and still more preferably less than 7.0%.
La2O3Component (B) La may be used2O3、La(NO3)3·XH2O (X is an arbitrary integer), and the like as a raw material.
Gd2O3Component (B) and (Y)2O3Component (B) and Yb2O3When the component (b) is an arbitrary component, and the content of at least one of the components is more than 0%, the refractive index of the glass can be increased while maintaining a desired abbe number, and resistance to devitrification can be improved.
On the other hand, by adding Gd2O3Component (B) and Yb2O3The content of each component is 15.0% or less, and devitrification due to the excessive content of these components can be reduced and the material cost of the glass can be suppressed. Thus, Gd2O3Component (B) and Yb2O3The content of each component is preferably 15.0% or less, more preferably less than 12.0%, and still more preferably less than 10.0%.
In addition, by adding Y2O3The content of the component is 15.0% or less, and devitrification due to the excessive content of the component can be reduced and the increase in abbe number can be suppressed. Thus, Y2O3The content of the component (b) is preferably 15.0% or less, more preferably less than 10.0%, and still more preferably less than 5.0%.
Gd2O3Component (B) and (Y)2O3Component (B) and Yb2O3As the component (B), Gd may be used2O3、GdF3、Y2O3、YF3、Yb2O3And the like as a raw material.
ZrO2When the component (b) is an arbitrary component and the content thereof is more than 0%, the rate of decrease in acid resistance can be reduced.
On the other hand, by mixing ZrO2The content of the component is 10.0% or less, and the excessive content of ZrO can be suppressed while maintaining a desired Abbe number2The resistance to devitrification by the component (B) is lowered. Thus, ZrO2The content of the component (b) is preferably 10.0% or less, more preferably less than 5.0%, and still more preferably less than 3.0%.
ZrO2Component (b) ZrO may be used2、ZrF4And the like as a raw material.
Nb2O5The component is any component, and when the content of the component is more than 0%, the acid resistance is improved.
On the other hand, by mixing Nb2O5The content of the component (A) is 10.0% or less, and therefore, the Abbe number can be kept low, and the reduction rate of acid resistance can be reduced, so that Nb2O5The content of the component (b) is preferably 10.0% or less, more preferably 8.0% or less, still more preferably 7.0% or less, still more preferably less than 5.0%, and still more preferably less than 3.0%.
Nb2O5Component (B) can be Nb2O5And the like as a raw material.
WO3When the component (b) is an arbitrary component and the content thereof is more than 0%, the refractive index is increased, the abrasion degree is reduced, and the devitrification resistance can be improved.
On the other hand, by mixing WO3The content of the component (b) is 10.0% or less, and the transmittance of the glass to visible light is less likely to decrease, and the material cost can be suppressed. Thus, WO3The content of the component (b) is preferably 10.0% or less, more preferably less than 7.0%, still more preferably less than 5.0%, still more preferably less than 3.0%, and still more preferably less than 1.0%.
WO3As the component (B), WO can be used3And the like as a raw material.
TiO2The component is optional, and when its content is greater than 0%, the content is reducedLow acid resistance.
On the other hand, by mixing TiO2The content of the component (A) is 10.0% or less, and a stable glass can be obtained while maintaining a low Abbe number. Thus, TiO2The content of the component (b) is preferably 10.0% or less, more preferably less than 5.0%, and still more preferably less than 3.0%.
TiO2Component (C), TiO can be used2And the like as a raw material.
Ta2O5When the component (b) is an arbitrary component and the content thereof is more than 0%, the refractive index can be increased, the devitrification resistance can be improved, and the viscosity of the molten glass can be improved.
On the other hand, by mixing Ta2O5The content of the component (A) is set to 5.0% or less, because Ta which is a rare mineral resource is reduced2O5The material cost of the glass can be reduced due to the use amount of the components. Thus, Ta2O5The content of the component (b) is preferably 5.0% or less, more preferably less than 3.0%, still more preferably less than 1.0%, and further preferably not contained.
Ta2O5Component (C) may be Ta2O5And the like as a raw material.
Li2The component O is an optional component, and when the content thereof is more than 0%, the meltability of the glass is improved and the refractive index is increased. Thus, Li2The content of the O component is preferably more than 0%, more preferably more than 0.5%.
On the other hand, by mixing Li2The content of the O component is 10.0% or less, and therefore devitrification can be reduced and the viscosity of the molten glass can be improved, and therefore, the occurrence of glass grain can be reduced. Thus, Li2The content of the O component is preferably 10.0% or less, more preferably less than 8.0%, and still more preferably less than 5.0%.
Li2O component, Li may be used2CO3、LiNO3LiF, etc. as raw materials.
Na2O component and K2The content of at least one of the O components is more than 0%, whereby the meltability of the glass raw material can be improved and the glass raw material can be obtainedThe resistance to devitrification can be improved.
On the other hand, by mixing Na2O component and K2The content of the O component is 10.0% or less, respectively, and thus the refractive index can be made difficult to decrease, and devitrification due to excessive content can be reduced. Thus, Na2O component and K2The content of the O component is preferably 10.0% or less, more preferably less than 8.0%, and still more preferably less than 5.0%, respectively.
Na2O component and K2As the O component, Na can be used2CO3、NaNO3、NaF、Na2SiF6、K2CO3、KNO3、KF、KHF2、K2SiF6And the like as a raw material.
GeO2When the component (b) is an arbitrary component and the content thereof is more than 0%, the refractive index of the glass can be increased and devitrification resistance can be improved.
However, due to GeO2The raw material (2) is expensive, and if the amount of the raw material is large, the material cost increases. Thus, GeO2The content of the component (b) is preferably 10.0% or less, more preferably less than 5.0%, still more preferably less than 3.0%, further preferably less than 1.0%, and further preferably none.
GeO2Component (C) GeO may be used2And the like as a raw material.
Al2O3When the component (b) is an arbitrary component and the content thereof is more than 0%, the rate of decrease in acid resistance is reduced and resistance to devitrification can be improved. Thus, Al2O3The content of the component (b) is preferably more than 0%, more preferably more than 1.5%, still more preferably more than 2.0%.
On the other hand, by mixing Al2O3The content of the component (A) is 10.0% or less, and devitrification due to excessive content can be suppressed. Thus, Al2O3The content of the component (b) is preferably 10.0% or less, more preferably less than 8.0%, and still more preferably less than 5.0%.
Al2O3Component (C) may be Al2O3、Al(OH)3、AlF3Etc. as the originalAnd (5) feeding.
Ga2O3When the component (b) is an optional component and the content thereof is more than 0%, chemical durability and resistance to devitrification can be improved.
On the other hand, by mixing Ga2O3The content of the component (A) is 10.0% or less, and devitrification due to excessive content can be reduced. Thus, Ga2O3The content of the component (b) is preferably 10.0% or less, more preferably less than 5.0%, still more preferably less than 3.0%, and further preferably less than 1.0%.
Ga2O3Component (b) Ga is used2O3And the like as a raw material.
Bi2O3The component is any component, and when the content of the component is more than 0%, the refractive index can be improved, the Abbe number can be reduced, and the glass transfer point can be reduced.
On the other hand, by adding Bi2O3When the content of the component (c) is 10.0% or less, the devitrification resistance of the glass can be improved, and the visible light transmittance can be improved by reducing the coloring of the glass. Thus, Bi2O3The content of the component (b) is preferably 10.0% or less, more preferably less than 5.0%, still more preferably less than 3.0%, and further preferably less than 1.0%.
Bi2O3Component (B) can use Bi2O3And the like as a raw material.
TeO2The component is any component, and when the content of the component is more than 0%, the refractive index can be improved, and the glass transfer point can be reduced.
On the other hand, by mixing TeO2The content of the component (A) is 10.0% or less, so that the coloring of the glass can be reduced and the visible light transmittance can be improved. Further, when a crucible made of platinum or a melting tank in which a portion in contact with molten glass is formed of platinum is used to melt a glass raw material, TeO exists2There is a problem that the composition may be alloyed with platinum. Thus, TeO2The content of the component (b) is preferably 10.0% or less, more preferably less than 5.0%, still more preferably less than 3.0%, and further preferably less than 1.0%.
TeO2Component (C) TeO can be used2And the like as a raw material.
SnO2When the component (b) is an optional component and the content thereof is more than 0%, the dissolution of platinum can be suppressed by reducing the oxidation of the molten glass, and the clarity of the molten glass can be promoted.
On the other hand, by adding SnO2The content of the component (c) is 3.0% or less, and the coloring of glass or devitrification of glass due to the reduction of molten glass can be reduced. Furthermore, since SnO2Alloying of the components with melting equipment (particularly, noble metal such as Pt) is reduced, and it is expected that the service life of the melting equipment will be extended. Thus, SnO2The content of the component (b) is preferably 3.0% or less, more preferably less than 1.0%, and still more preferably less than 0.5%.
SnO2As the component (C), SnO or SnO can be used2、SnF2、SnF4And the like as a raw material.
Sb2O3When the component (b) is an optional component and the content thereof is more than 0%, the molten glass can be defoamed.
On the other hand, if Sb2O3When the content of the component is too large, transmittance in a short wavelength region of a visible light region is deteriorated. Thus, Sb2O3The content of the component (b) is preferably 1.0% or less, more preferably less than 0.5%, and still more preferably less than 0.1%.
Sb2O3Component (C), Sb may be used2O3、Sb2O5、Na2H2Sb2O7·5H2O and the like as raw materials.
Further, the component for refining and defoaming the glass is not limited to the above-mentioned Sb2O3As the component (b), a clarifier, a defoaming agent or a combination thereof well known in the art of glass production can be used.
The component F is an arbitrary component, and when the content thereof is more than 0%, the Abbe number of the glass can be increased, the glass transfer point can be lowered, and the devitrification resistance can be improved.
However, if the content of the F component, that is, the total amount of F of the fluoride in which a part or all of 1 or 2 or more oxides of the above elements are replaced is more than 10.0%, the volatilization amount of the F component increases, and therefore it becomes difficult to obtain stable optical constants, and it becomes difficult to obtain homogeneous glass. In addition, the abbe number may increase to a greater extent than desired.
Therefore, the content of the F component is preferably 10.0% or less, more preferably less than 5.0%, still more preferably less than 3.0%, and further preferably less than 1.0%.
Component F can be prepared by, for example, using ZrF4、AlF3、NaF、CaF2And the like as raw materials contained in the glass.
The sum (mass sum) of the contents of RO components (wherein R is1 or more selected from the group consisting of Mg, Ca, Sr, Ba) is preferably 10.0% to 50.0%.
In particular, by setting the sum to 10% or more, the refractive index can be increased, and the resistance to devitrification of the glass can be improved. Therefore, the total content of RO components is preferably 10% or more, more preferably more than 15.0%, still more preferably 18.0% or more, still more preferably 20.0% or more, and still more preferably more than 23.0%.
On the other hand, by setting the sum to 50.0% or less, devitrification due to the excessive content of these components can be reduced, and glass with a small reduction rate of acid resistance and a small degree of abrasion can be obtained. Therefore, the total content of RO components is preferably 50.0% or less, more preferably 45.0% or less, still more preferably 42.0% or less, and still more preferably 40.0% or less.
Rn2The sum (mass sum) of the contents of the O components (Rn is1 or more selected from the group consisting of Li, Na, and K in the formula) is preferably 15.0% or less. This can suppress lowering of the refractive index of the glass and reduce devitrification. Thus, Rn2The sum of the contents of the O components is preferably 15.0% by mass or less, more preferably less than 10.0%, still more preferably less than 8.0%, and still more preferably less than 5.0%.
Ln2O3The sum (mass sum) of the contents of the components (in the formula, Ln is1 or more selected from the group consisting of La, Gd, Y and Yb), preferably 20.0% or less.
In particular, by setting the sum of the masses to 20.0% or less, the stability of the glass can be improved and the devitrification resistance of the glass can be improved. Thus, Ln2O3The sum of the contents of the components is preferably 20.0% by mass or less, more preferably 15.0% by mass or less, and still more preferably 13.0% by mass or less.
The ratio (mass ratio) of the content of the SrO component to the content of the BaO component is preferably greater than 0. This makes it possible to obtain glass having a desired Abbe number, a small reduction rate of acid resistance, and a small abrasion degree. Therefore, the mass ratio (SrO/BaO) is preferably more than 0, more preferably more than 0.10, still more preferably more than 0.20, further preferably more than 0.30, and still further preferably more than 0.42.
On the other hand, the mass ratio (SrO/BaO) is preferably less than 15.0, more preferably less than 14.0, and still more preferably less than 13.0.
BaO component and Gd2O3The sum (mass sum) of the contents of the components is preferably more than 0% and 50.0% or less.
In particular, by setting the sum to more than 0%, it is possible to obtain glass having a small reduction rate of acid resistance and a small degree of abrasion while maintaining a desired abbe number. Therefore, the mass sum of (BaO + Gd)2O3) Preferably greater than 0%, more preferably greater than 0.05%, still more preferably greater than 1.0%, and still more preferably greater than 1.5%.
On the other hand, by adding the mass to (BaO + Gd)2O3) By setting the refractive index to 50.0% or less, the glass can be stabilized while reducing the degree of abrasion while having a desired refractive index. The sum of mass and (BaO + Gd)2O3) Preferably 50.0% or less, more preferably less than 40.0%, still more preferably less than 35.0%, still more preferably less than 30.0%, and still more preferably less than 24.5%.
< ingredients that should not be contained >
Next, components that should not be contained in the optical glass of the present invention and components that are not suitable to be contained therein will be described.
Other components may be added as required within the range not affecting the characteristics of the glass of the present invention. However, when various transition metal components such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo are contained alone or in a composite form in addition to Ti, Zr, Nb, W, La, Gd, Y, Yb and Lu, the glass is colored even if contained in a small amount, and the absorption is generated for a specific wavelength in the visible region, and therefore, it is preferable that the glass is substantially not contained particularly in an optical glass using a wavelength in the visible region.
Further, lead compounds such As PbO and As2O3The arsenic compound is a component having a high environmental load, and therefore, it is preferable not to substantially contain, that is, except for unavoidable mixing, any of these components.
In addition, since each of Th, Cd, Tl, Os, Be and Se is considered to Be a harmful chemical substance in recent years and tends to Be avoided, it is necessary to dispose of the chemical substance not only in the glass production step but also in the processing step and the treatment after the product formation in accordance with environmental measures. Therefore, when importance is attached to the environmental influence, it is preferable that these components are not substantially contained.
[ production method ]
The optical glass of the present invention can be produced, for example, in the following manner. That is, a method in which the above-mentioned raw materials are uniformly mixed within a predetermined content range, the resulting mixture is put into a platinum crucible, a quartz crucible or an aluminum crucible to be preliminarily melted, then put into a platinum crucible, a platinum alloy crucible or an iridium crucible to be melted at a temperature ranging from 1100 ℃ to 1400 ℃ over 1 hour to 5 hours, the mixture is stirred to be homogenized and defoamed, and then the temperature is lowered to 1000 ℃ to 1300 ℃, followed by stirring at the final stage to remove the texture, and the mixture is cast into a mold and slowly cooled.
[ Properties ]
The optical glass of the present invention has a high refractive index and a high Abbe number (low dispersion).
In particular, the refractive index (n) of the optical glass of the present inventiond) The lower limit thereof is preferably 1.55 or more, more preferably 1.56The above is still more preferably 1.57 or more. The upper limit of the refractive index is preferably 1.70 or less, more preferably 1.65, and still more preferably 1.63.
Further, the Abbe number (. nu.) of the optical glass of the present inventiond) The lower limit thereof is preferably 45 or more, more preferably 50 or more, still more preferably 55 or more, and further preferably 60 or more. The upper limit of the abbe number is preferably 75 or less, more preferably 73 or less, and still more preferably less than 70.
The optical glass of the present invention has the refractive index and the abbe number as described above, and therefore, can exhibit an effect in optical design, and in particular, can achieve miniaturization of an optical system in addition to the expectation of high imaging characteristics, etc., and thus, can increase the degree of freedom in optical design.
The optical glass of the present invention preferably has high acid resistance. In particular, the chemical durability (acid resistance) of the glass powder method according to JOGIS 06-2009 is preferably grade 1 to grade 5, more preferably grade 2 to grade 4, and still more preferably grade 3 to grade 4.
With this, in addition to improving the processability of the optical glass, when used in automotive applications and the like, fogging of the glass due to acid rain and the like is reduced, and an optical element formed of the glass can be more easily manufactured.
Here, "acid resistance" refers to the resistance to corrosion of glass by acid, and the acid resistance can be measured according to japanese optical glass industry association standard "method for measuring chemical durability of optical glass" JOGIS 06-2009. Further, "chemical durability (acid resistance) according to the powder method is class 1 to class 3" means that the chemical durability (acid resistance) according to JOGIS 06-2009 is less than 0.65% by mass in terms of the rate of decrease in the mass of the sample before and after measurement.
Further, "grade 1" of chemical durability (acid resistance) means that the mass loss rate of the sample before and after the measurement is less than 0.20 mass%, "grade 2" means that the mass loss rate of the sample before and after the measurement is 0.20 mass% or more and less than 0.35 mass%, "grade 3" means that the mass loss rate of the sample before and after the measurement is 0.35 mass% or more and less than 0.65 mass%, "grade 4" means that the mass loss rate of the sample before and after the measurement is 0.65 mass% or more and less than 1.20 mass%, "grade 5" means that the mass loss rate of the sample before and after the measurement is 1.20 mass% or more and less than 2.20 mass%, and "grade 6" means that the mass loss rate of the sample before and after the measurement is 2.20 mass% or more.
In addition, the optical glass of the present invention is preferably low in abrasion. The abrasion resistance of the optical glass of the present invention is preferably 480, more preferably 450, still more preferably 430 in its upper limit.
The abrasion degree is a value measured by "abrasion degree measuring method for optical glass according to JOGIS 10-1994".
The optical glass of the present invention preferably has a low coloring because it has a high transmittance of visible light, particularly, a high transmittance of light on the short wavelength side of visible light.
In particular, the optical glass of the present invention has a wavelength (. lamda.) of 80% spectral transmittance in a sample having a thickness of 10mm, as expressed by the transmittance of the glass80) The upper limit is preferably 420nm, more preferably 410nm, and still more preferably 400 nm.
In addition, in the optical glass of the present invention, the shortest wavelength (. lamda.) of 5% of the spectral transmittance is shown in a sample having a thickness of 10mm5) The upper limit is preferably 380nm, more preferably 370nm, and still more preferably 360 nm.
This makes it possible to improve the transparency of the glass to visible light by making the absorption edge of the glass near the ultraviolet region, and therefore, the optical glass can be suitably used for an optical element that transmits light, such as a lens.
[ glass Molding and optical element ]
The glass shaped body can be produced from the optical glass produced by, for example, polishing or press molding such as reheat press molding or precision press molding. That is, the glass molded body can be produced in the following manner: machining optical glass by grinding, polishing, etc. to produce a glass molded body; a step of producing a glass molded body by subjecting a preform made of optical glass to reheat press molding and then to polishing processing; a glass shaped body or the like is produced by precision press molding a preform produced by polishing or a preform formed by known float molding or the like. The method for producing the glass shaped material is not limited to the above.
As described above, the glass molded body formed of the optical glass of the present invention can exhibit effects in various optical elements and optical designs, and is particularly suitable for use in optical elements such as lenses and prisms. Accordingly, a glass molded body having a large diameter can be formed, and therefore, in addition to the desired increase in size of the optical element, when used in an optical device such as a camera or a projector, high-definition and high-precision image forming characteristics and projection characteristics can be realized.
[ examples ]
Compositions and refractive indices (n) of examples (Nos. 1 to 70) and comparative examples of the present inventiond) Abbe number (. nu.) ]d) Acid resistance, abrasion resistance, and wavelengths (lambda) representing spectral transmittances of 5% and 80%5、λ80) All are shown in tables 1 to 10.
In addition, the following examples are for illustrative purposes only, and the present invention is not limited to these examples.
The glasses of examples and comparative examples were prepared by selecting high-purity raw materials used for general optical glasses such as oxides, hydroxides, carbonates, nitrates, fluorides, metaphosphoric acid compounds, etc. corresponding to the above raw materials, weighing the raw materials so as to have the composition ratios shown in the tables of examples and comparative examples, uniformly mixing the raw materials, putting the raw materials into a quartz crucible or a platinum crucible, melting the raw materials in an electric furnace set to a temperature range of 1100 ℃ to 1400 ℃ depending on the ease of melting of the glass composition for 1 hour to 5 hours, stirring the molten materials to homogenize the molten materials and defoam the molten materials, cooling the molten materials to a temperature of 1000 ℃ to 1300 ℃, stirring the homogenized materials, casting the molten materials into a mold, and gradually cooling the mold.
Refractive index (n) of glasses of examples and comparative examplesd) And Abbe number (v)d) Expressed as a measurement of the d-line (587.56nm) for a helium lamp. In addition, Abbe number (v)d) Using the above d-lineRefractive index of (2), refractive index (n) of F-line (486.13nm) for hydrogen lampF) Refractive index (n) for C line (656.27nm)C) By the Abbe number (v)d)＝[(nd-1)/(nF-nC)]Is calculated by the numerical expression.
Further, the acid resistance of the glasses of the examples and comparative examples was measured according to the Japanese Industrial Association for optical glass Standard "method for measuring chemical durability of optical glass" JOGIS 06-2009. That is, a glass sample crushed to a particle size of 425 μm to 600 μm was put into a platinum basket as a specific weight gram. The platinum basket was placed in a quartz glass round bottom flask containing 0.01N nitric acid in water and treated in a boiling water bath for 60 minutes. The reduction rate (% by mass) of the treated glass sample was calculated, and the reduction rate (% by mass) was rated 1 when it was less than 0.20, rated 2 when it was from 0.20 to less than 0.35, rated 3 when it was from 0.35 to less than 0.65, rated 4 when it was from 0.65 to less than 1.20, rated 5 when it was from 1.20 to less than 2.20, and rated 6 when it was more than 2.20. In this case, the smaller the number of steps, the more preferable the acid resistance of the glass.
In addition, the degree of abrasion was measured according to "JOGIS 10-1994 method for measuring degree of abrasion of optical glass". That is, a sample of a glass square plate having a size of 30X 10mm was placed at a fixed position 80mm from the center of a cast iron plane plate (250 mm. phi.) horizontally rotating at a rotation speed of 60rpm, a load of 9.8N (1kgf) was vertically applied, and 10g of a polishing liquid to which abrasive material #800 (average particle diameter 20 μm) was added (alumina A abrasive grains) was uniformly supplied in 20mL of water and polished for 5 minutes, and the mass of the sample before and after polishing was measured to determine the abrasion mass. Similarly, the abrasion quality of a standard sample specified by the japan optical glass industry was obtained and calculated according to the following formula.
Degree of abrasion { (abrasion mass/specific gravity of sample)/(abrasion mass/specific gravity of standard sample) } × 100
The transmittance of the glass of the examples was measured in accordance with the Japanese society for optical glass specification JOGIS 02-2003. In addition, in the invention, the presence or absence of coloring and the coloring course of the glass are obtained by measuring the transmittance of the glassAnd (4) degree. Specifically, a polishing article having a thickness of 10. + -. 0.1mm is made relatively parallel to each other, and the spectroscopic transmittance at 200nm to 800nm is measured in accordance with JIS Z8722 to determine λ5(wavelength at 5% transmittance) and lambda80(wavelength at which the transmittance is 80%).
[ TABLE 1 ]
[ TABLE 2 ]
[ TABLE 3 ]
[ TABLE 4 ]
[ TABLE 5 ]
[ TABLE 6 ]
[ TABLE 7 ]
[ TABLE 8 ]
[ TABLE 9 ]
[ TABLE 10 ]
As shown in these tables, the refractive index (n) of the optical glass of the examples of the present invention was whateverd) All of 1.55 or more, more specifically 1.57 or more, and the refractive index (n)d) Also, 1.70 or less, more specifically, 1.63 or less, are within the desired range.
In addition, the Abbe number (. nu.) of the optical glass of the embodiment of the present invention, whichever isd) All 45 or more, more specifically 50 or more, and still more specifically 60 or more, and the Abbe number (. nu.d) Also below 75, more particularly below 70, are all within the desired range.
Further, the optical glass of the embodiment of the present invention, λ80(wavelength at which the transmittance is 80%) is 550nm or less, more specifically 500nm or less. Further, the optical glass of the embodiment of the present invention, λ5(wavelength at a transmittance of 5%) is 400nm or less, more specifically 380nm or less. Therefore, it is clear that the optical glass of the embodiment of the present invention has high transmittance for visible light and is difficult to be colored.
The optical glass of the present invention is stable without devitrification.
In addition, the acid resistance of the optical glass of the embodiment of the present invention is in the range of 1 grade to 5 grades. On the other hand, the optical glass of the comparative example was found to have acid resistance of grade 6 and to be inferior in processability.
Therefore, it is clear that the light of the embodiments of the present inventionOptical glass, refractive index (n)d) And Abbe number (v)d) All within a desired range, and optical glass having acid resistance of grade 1 to grade 5 can be obtained.
Although the present invention has been described in detail for the purpose of illustration, the present embodiment is for illustrative purposes only, and it will be understood by those skilled in the art that various changes may be made without departing from the spirit and scope of the invention.
Claims (8)
1. An optical glass comprising, in mass%:
P2O5ingredient 35.0% to 65.0%;
B2O3the component is more than 0 percent and less than or equal to 20.0 percent;
BaO content is more than 0% and less than or equal to 30.0%;
SrO content is more than 0% and less than or equal to 35.0%; and
WO3the component is more than 0 percent and less than or equal to 10.0 percent;
the mass ratio (B) of the above optical glass2O3SrO) is greater than 0;
the optical glass has a refractive index (n)d)1.55 to 1.70, Abbe number (. nu.d)45 to 75, and has chemical durability/acid resistance according to the powder method of grade 1 to grade 5.
2. The optical glass according to claim 1,
SiO2the component is 0% to 10.0%;
MgO component is 0% to 15.0%;
CaO component is 0% to 15.0%;
the ZnO component is 0% to 25.0%;
La2O3the component is 0% to 15.0%;
Gd2O3the component is 0% to 15.0%;
Y2O3the component is 0% to 15.0%;
Yb2O3the component is 0% to 15.0%;
ZrO2the component is 0% to 10.0%;
Nb2O5the component is 0% to 10.0%;
TiO2the component is 0% to 10.0%;
Ta2O5the component is 0% to 5.0%;
Li2the O component is 0% to 10.0%;
Na2the O component is 0% to 10.0%;
K2the O component is 0% to 10.0%;
GeO2the component is 0% to 10.0%;
Al2O3the component is 0% to 10.0%;
Ga2O3the component is 0% to 10.0%;
Bi2O3the component is 0% to 10.0%;
TeO2the component is 0% to 10.0%;
SnO2the component is 0% to 3.0%;
Sb2O3the component is 0% to 1.0%;
the content of F as a fluoride in which a part or all of 1 or 2 or more oxides of the above elements are substituted is0 to 10.0% by mass.
3. The optical glass according to claim 1 or 2, wherein the glass composition comprises, in mass%,
the sum of the contents of RO components is 10.0% to 50.0%, wherein R is more than 1 selected from the group consisting of Mg, Ca, Sr and Ba;
Rn2the sum of the contents of O components is 15.0% or less, wherein Rn is1 or more selected from the group consisting of Li, Na and K;
Ln2O3the total amount of the components is 20.0% or less, wherein Ln is1 or more selected from the group consisting of La, Gd, Y and Yb.
4. The optical glass as claimed in any one of claims 1 to 3, wherein a mass ratio (SrO/BaO) is more than 0 to less than 15.0.
5. The optical glass as defined in any one of claims 1 to 4 wherein the mass sum (BaO + Gd)2O3) Is more than 0% to less than 50.0%.
6. A preform made of the optical glass as defined in any one of claims 1 to 5.
7. An optical element comprising the optical glass according to any one of claims 1 to 5.
8. An optical device comprising the optical element according to claim 7.
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| JP2016-237890 | 2016-12-07 | ||
| JP2016237890 | 2016-12-07 | ||
| CN201780075208.1A CN110114321A (en) | 2016-12-07 | 2017-11-01 | Optical glass, preform and optical element |
| PCT/JP2017/039487 WO2018105279A1 (en) | 2016-12-07 | 2017-11-01 | Optical glass, preform, and optical element |
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| CN114853336A (en) * | 2022-06-22 | 2022-08-05 | 成都光明光电股份有限公司 | Optical glass, glass preform, optical element and optical instrument |
| CN116239301A (en) * | 2023-03-07 | 2023-06-09 | 上海太洋科技有限公司 | Phosphate optical glass and preparation method thereof |
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| WO2020017275A1 (en) * | 2018-07-18 | 2020-01-23 | 株式会社オハラ | Optical glass, preform and optical element |
| CN110204192B (en) * | 2019-06-28 | 2021-09-28 | 中国建筑材料科学研究总院有限公司 | Deep ultraviolet transparent phosphate glass and preparation method and application thereof |
| CN111960669A (en) * | 2020-08-31 | 2020-11-20 | 湖北新华光信息材料有限公司 | Low specific gravity phosphorus crown optical glass for precision mould pressing, preparation method of raw materials thereof and optical element |
| CN113003935B (en) * | 2021-02-07 | 2022-08-26 | 湖北新华光信息材料有限公司 | Fluorophosphate optical glass, preparation method thereof and optical element |
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Also Published As
| Publication number | Publication date |
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| JPWO2018105279A1 (en) | 2019-10-24 |
| CN110114321A (en) | 2019-08-09 |
| TWI746722B (en) | 2021-11-21 |
| WO2018105279A1 (en) | 2018-06-14 |
| JP7075895B2 (en) | 2022-05-26 |
| TW201834991A (en) | 2018-10-01 |
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