TW202402695A - Optical glass, preform, and optical element - Google Patents
Optical glass, preform, and optical element Download PDFInfo
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- 239000005304 optical glass Substances 0.000 title claims abstract description 80
- 230000003287 optical effect Effects 0.000 title claims abstract description 34
- 238000002834 transmittance Methods 0.000 claims abstract description 32
- 230000003595 spectral effect Effects 0.000 claims abstract description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 50
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 29
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 26
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 17
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 9
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 7
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 7
- 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
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 239000011521 glass Substances 0.000 abstract description 118
- 239000006185 dispersion Substances 0.000 abstract description 49
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 6
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 238000004031 devitrification Methods 0.000 description 43
- 239000002994 raw material Substances 0.000 description 40
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 238000004040 coloring Methods 0.000 description 13
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 239000006060 molten glass Substances 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- -1 As 2 O 3 Chemical class 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910005690 GdF 3 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910008449 SnF 2 Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229940093920 gynecological arsenic compound Drugs 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000010438 heat treatment 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
- 230000006872 improvement Effects 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
- 150000002611 lead compounds Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 238000002156 mixing Methods 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
- 230000010494 opalescence Effects 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C03C3/04—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
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
-
- 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
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/18—Stirring devices; Homogenisation
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Glass Compositions (AREA)
- Eyeglasses (AREA)
Abstract
Description
本發明是關於光學玻璃、預成形體及光學元件。The present invention relates to optical glass, preforms and optical elements.
近年,使用光學系統之機器的數位化,以及圖像、影像的高清晰化正急速地發展。尤其是圖像、影像的高清晰化,在數位相機或錄影機、投影機等光學機器,極為顯著。此外,在這同時,藉由削減內藏於這些光學機器的光學系統中之光學元件的數量,像是透鏡或稜鏡等,來達成輕量化、小型化。In recent years, the digitization of machines using optical systems and the improvement of high-definition images and videos have been rapidly developed. In particular, the high-definition of images and videos is extremely noticeable in optical equipment such as digital cameras, video recorders, and projectors. In addition, at the same time, weight reduction and miniaturization can be achieved by reducing the number of optical components, such as lenses or lenses, built into the optical systems of these optical machines.
製作光學元件的光學玻璃之中,特別是對於具有1.90以上的高折射率(n d),15.0以上30.0以下的低阿貝數(ν d)之高折射率高色散玻璃的需求變高,因為該種光學玻璃能夠達到使光學系統整體輕量化及小型化。作為這種高折射率低色散玻璃,已知如專利文獻1所代表的玻璃組成物。 [先前技術文獻] [專利文獻] Among optical glasses for making optical elements, the demand for high refractive index and high dispersion glass with a high refractive index (n d ) of 1.90 or more and a low Abbe number (ν d ) of 15.0 or more and 30.0 or less is particularly high, because This kind of optical glass can make the overall optical system lighter and smaller. As such high refractive index and low dispersion glass, a glass composition represented by Patent Document 1 is known. [Prior art documents] [Patent documents]
[專利文獻1]日本特開2011-178571號公報。[Patent Document 1] Japanese Patent Application Publication No. 2011-178571.
[發明所欲解決之課題][Problem to be solved by the invention]
然而,專利文獻1所記載之玻璃,為了促進高折射率高色散化,GeO 2成分、Nb 2O 5成分及Ta 2O 5成分等材料單價高的成分的含量較多,有生產成本變高這樣的問題存在。因此,期望出現一種不僅具有高折射率/高色散,且表示分光透過率5%之波長(λ 5)短,生產成本低的光學玻璃。 However, in order to promote high refractive index and high dispersion, the glass described in Patent Document 1 contains a large amount of components with high unit price, such as GeO 2 components, Nb 2 O 5 components, and Ta 2 O 5 components, which may increase the production cost. Such problems exist. Therefore, it is desired to have an optical glass that not only has high refractive index/high dispersion, but also has a short wavelength (λ 5 ) indicating a spectral transmittance of 5% and has low production cost.
有鑑於上述的問題點,本發明之目的在於提供一種具有高折射率及表示分光透過率5%之波長(λ 5)短,且生產成本低的光學玻璃,以及使用該光學玻璃之預成形體與光學元件。 [用以解決課題之手段] In view of the above problems, the object of the present invention is to provide an optical glass that has a high refractive index, a short wavelength (λ 5 ) indicating a spectral transmittance of 5%, and low production cost, and a preform using the optical glass. with optical components. [Means used to solve problems]
本發明人等,為了解決上述課題,專注累積試驗研究的結果,發現藉由一邊併用La 2O 3成分、TiO 2成分、及BaO成分,一邊調整SiO 2成分與B 2O 3成分的合計量,或是TiO 2/(TiO 2+BaO)的質量比,可獲得期望的高折射率及高色散,並降低生產成本,且表示分光透過率5%之波長(λ 5)變短,遂完成本發明。 具體而言,本發明提供下述之物。 In order to solve the above-mentioned problems, the present inventors concentrated on accumulating the results of experimental studies and found that the total amount of the SiO 2 component and the B 2 O 3 component can be adjusted by using the La 2 O 3 component, the TiO 2 component, and the BaO component together. , or the mass ratio of TiO 2 / (TiO 2 + BaO), can obtain the desired high refractive index and high dispersion, and reduce production costs, and the wavelength (λ 5 ) indicating 5% spectral transmittance is shortened, and it is completed invention. Specifically, the present invention provides the following.
(1)一種光學玻璃,其中,以氧化物基準的質量%計,含有La 2O 3成分大於0%至45.0%、TiO 2成分大於0%至45.0%、及BaO成分大於0%至40.0%;並含有SiO 2成分與B 2O 3成分的合計量是5.0%以上30.0%以下;TiO 2/(TiO 2+BaO)的質量比是0.10以上0.90以下;折射率(n d)是1.90以上,阿貝數(ν d)是30.0以下,且表示分光透過率5%之波長(λ 5)為400nm以下。 (1) An optical glass containing a La 2 O 3 component of more than 0% to 45.0%, a TiO 2 component of more than 0% to 45.0%, and a BaO component of more than 0% to 40.0% in mass % on an oxide basis ; and the total amount of the SiO 2 component and the B 2 O 3 component is 5.0% or more and 30.0% or less; the mass ratio of TiO 2 /(TiO 2 +BaO) is 0.10 or more and 0.90 or less; the refractive index (n d ) is 1.90 or more , the Abbe number (ν d ) is 30.0 or less, and the wavelength (λ 5 ) indicating 5% spectral transmittance is 400 nm or less.
(2)如(1)所述之光學玻璃,其中以氧化物基準的質量%計,SiO 2成分是0%至30.0%,及B 2O 3成分是0%至30.0%。 (2) The optical glass as described in (1), wherein the SiO 2 component is 0% to 30.0%, and the B 2 O 3 component is 0% to 30.0% in mass % on an oxide basis.
(3)如(1)或(2)所述之光學玻璃,其中以氧化物基準的質量%計,ZnO成分是0%至20.0%,Y 2O 3是0%至15.0%,Nb 2O 5成分是0%至25.0%,Yb 2O 3成分是0%至15.0%,及Gd 2O 3成分是0%至15.0%。 (3) The optical glass as described in (1) or (2), in which the ZnO component is 0% to 20.0%, Y 2 O 3 is 0% to 15.0%, and Nb 2 O is the mass % of the oxide basis. The 5 component is 0% to 25.0%, the Yb 2 O 3 component is 0% to 15.0%, and the Gd 2 O 3 component is 0% to 15.0%.
(4)如(1)至(3)中任一項之光學玻璃,其中以氧化物基準的質量%計,(La 2O 3+Nb 2O 5+Gd 2O 3+Yb 2O 3)的質量和是大於0%且60.0%以下。 (4) The optical glass according to any one of (1) to (3), in which in terms of mass % based on oxide, (La 2 O 3 +Nb 2 O 5 +Gd 2 O 3 +Yb 2 O 3 ) The sum of the masses is greater than 0% and less than 60.0%.
(5)如(1)至(4)中任一項之光學玻璃,其中以氧化物基準的質量%計,Ln 2O 3成分(式中,Ln是選自La、Gd、Y、Yb所成群組中的1種以上)的合計量是大於0%且50.0%以下。 (5) The optical glass according to any one of (1) to (4), in which the Ln 2 O 3 component (in the formula, Ln is selected from the group consisting of La, Gd, Y, and Yb) is calculated as mass % on an oxide basis. The total amount of more than 1 species in the group is greater than 0% and less than 50.0%.
(6)如(1)至(5)中任一項之光學玻璃,以氧化物基準計,TiO 2/BaO的質量比是大於0且3.00以下。 (6) In the optical glass according to any one of (1) to (5), the mass ratio of TiO 2 /BaO is greater than 0 and less than 3.00 on an oxide basis.
(7)如(1)至(6)中任一項之光學玻璃,其中以氧化物基準的質量%計,Rn 2O成分(式中,Rn是選自Li、Na、K所成群組中的1種以上)的質量和是15.0%以下。 (7) The optical glass according to any one of (1) to (6), in which the Rn 2 O component (in the formula, Rn is selected from the group consisting of Li, Na, and K) is calculated as mass % on an oxide basis. The sum of the mass of more than 1 of them) is less than 15.0%.
(8)如(1)至(7)中任一項之光學玻璃,其中以氧化物基準的質量%計,RO成分(式中,R是選自Mg、Ca、Sr、Ba、Zn所成群組中的1種以上)的質量和是大於0%且35.0%以下。(8) The optical glass according to any one of (1) to (7), in which the RO component (in the formula, R is selected from the group consisting of Mg, Ca, Sr, Ba, and Zn) is calculated as mass % on an oxide basis. The sum of the masses of more than 1 species in the group is greater than 0% and less than 35.0%.
(9)如(1)至(8)中任一項之光學玻璃,其中以氧化物基準的質量%計,其含有ZrO 2成分0%至20.0%、Nb 2O 5成分0%至15.0%、WO 3成分0%至10.0%、Ta 2O 5成分0%至10.0%、MgO成分0%至15.0%、CaO成分0%至15.0%、SrO成分0%至15.0%、Li 2O成分0%至15.0%、Na 2O成分0%至15.0%、K 2O成分0%至15.0%、P 2O 5成分0%至10.0%、GeO 2成分0%至10.0%、Al 2O 3成分0%至15.0%、Ga 2O 3成分0%至15.0%、Bi 2O 3成分0%至10.0%、TeO 2成分0%至10.0%、SnO 2成分0%至3.0%、及Sb 2O 3成分0%至1.0%。 (9) The optical glass according to any one of (1) to (8), which contains a ZrO 2 component of 0% to 20.0% and a Nb 2 O 5 component of 0% to 15.0% in terms of mass % on an oxide basis. , WO 3 component 0% to 10.0%, Ta 2 O 5 component 0% to 10.0%, MgO component 0% to 15.0%, CaO component 0% to 15.0%, SrO component 0% to 15.0%, Li 2 O component 0 % to 15.0%, Na 2 O component 0% to 15.0%, K 2 O component 0% to 15.0%, P 2 O 5 component 0% to 10.0%, GeO 2 component 0% to 10.0%, Al 2 O 3 component 0% to 15.0%, Ga 2 O 3 composition 0% to 15.0%, Bi 2 O 3 composition 0% to 10.0%, TeO 2 composition 0% to 10.0%, SnO 2 composition 0% to 3.0%, and Sb 2 O 3 ingredients 0% to 1.0%.
(10)一種預成形體,由(1)至(9)中任一項之光學玻璃而成。(10) A preform made of the optical glass according to any one of (1) to (9).
(11)一種光學元件,由(1)至(9)中任一項之光學玻璃而成。(11) An optical element made of the optical glass according to any one of (1) to (9).
(12)一種光學機器,具備如(11)所述之光學元件。 [發明功效] (12) An optical machine including the optical element according to (11). [Invention effect]
根據本發明,能夠提供一種不僅具有高折射率,且表示分光透過率5%之波長(λ 5)短,生產成本低的光學玻璃,以及使用該光學玻璃之預成形體與光學元件。 According to the present invention, it is possible to provide optical glass that not only has a high refractive index but also has a short wavelength (λ 5 ) indicating a spectral transmittance of 5% and has low production cost, as well as preforms and optical elements using the optical glass.
本發明的光學玻璃,以質量%計,含有La 2O 3成分大於0%至45.0%、TiO 2成分大於0%至45.0%、及BaO成分大於0%至40.0%;SiO 2成分與B 2O 3成分的合計量是5.0%以上30.0%以下;TiO 2/(TiO 2+BaO)的質量比是0.10以上0.90以下;折射率(n d)是1.90以上,阿貝數(ν d)是30.0以下,且表示分光透過率5%之波長(λ 5)為400nm以下。 根據本發明,藉由一邊併用La 2O 3成分、TiO 2成分、及BaO成分,一邊調整各成分的含量,可期望玻璃的高折射率及高色散化,並提高玻璃的安定性。因此,能夠提供一種不僅具有高折射率及高色散,且表示分光透過率5%之波長(λ 5)短,生產成本低的光學玻璃,以及使用該光學玻璃之預成形體與光學元件。 The optical glass of the present invention contains, in mass %, a La 2 O 3 component of greater than 0% to 45.0%, a TiO 2 component of greater than 0% to 45.0%, and a BaO component of greater than 0% to 40.0%; the SiO 2 component and B 2 The total amount of O 3 components is 5.0% or more and 30.0% or less; the mass ratio of TiO 2 /(TiO 2 +BaO) is 0.10 or more and 0.90 or less; the refractive index (n d ) is 1.90 or more, and the Abbe number (ν d ) is 30.0 or less, and the wavelength (λ 5 ) indicating 5% spectral transmittance is 400nm or less. According to the present invention, by adjusting the content of each component while using the La 2 O 3 component, the TiO 2 component, and the BaO component in combination, it is possible to expect a high refractive index and high dispersion of the glass, and to improve the stability of the glass. Therefore, it is possible to provide an optical glass that not only has high refractive index and high dispersion, but also has a short wavelength (λ 5 ) indicating a spectral transmittance of 5% and has low production cost, as well as preforms and optical elements using the optical glass.
[玻璃成分] 構成本發明之光學玻璃的各成分的組成範圍如下所述。本說明書中,各成分的含量在未特別否定時,皆是以相對於氧化物基準的玻璃全質量之質量%來表示。在此,「氧化物基準」是指,假設作為本發明的玻璃組成成分原料所使用的氧化物、複合鹽、金屬氟化物等在熔融時,全部分解變成氧化物的情況下,將該氧化物的總質量設為100質量%,來表示玻璃中所含有的各種成分之組成。 [Glass composition] The composition range of each component constituting the optical glass of the present invention is as follows. In this specification, unless otherwise specified, the content of each component is expressed in mass % relative to the total mass of the glass on an oxide basis. Here, the "oxide standard" refers to the case where all the oxides, complex salts, metal fluorides, etc. used as raw materials for the glass composition components of the present invention are decomposed into oxides during melting. The total mass of is set to 100% by mass to represent the composition of various components contained in the glass.
<關於必須成分、任意成分> La 2O 3成分,是一種可提高玻璃的折射率,減小色散之成分。尤其,藉由含有大於0%的La 2O 3成分,能夠獲得所期望的高折射率,為一種必須成分。因此,La 2O 3成分的含量,其下限以大於0%為佳,較佳是3.0%,更佳是15.0%,進而較佳是20.0%,進而更佳是25.0%,再進而更佳是27.0%。 另一方面,藉由將La 2O 3成分的含量設為45.0%以下,能夠提高玻璃的耐失透性,抑制玻璃的比重增加,且能夠降低生產成本。因此,La 2O 3成分的含量,其上限以45.0%為佳,較佳是40.0%,更佳是38.0%,進而更佳是37.0%。 La 2O 3成分,可使用La 2O 3、La(NO 3) 3・XH 2O(X為任意整數)等作為原料。 <About essential components and optional components> The La 2 O 3 component is a component that can increase the refractive index of glass and reduce dispersion. In particular, by containing more than 0% of the La 2 O 3 component, a desired high refractive index can be obtained, and it is an essential component. Therefore, the lower limit of the content of the La 2 O 3 component is preferably greater than 0%, preferably 3.0%, more preferably 15.0%, further preferably 20.0%, still more preferably 25.0%, still more preferably 27.0%. On the other hand, by setting the content of the La 2 O 3 component to 45.0% or less, the devitrification resistance of the glass can be improved, the increase in the specific gravity of the glass can be suppressed, and the production cost can be reduced. Therefore, the upper limit of the content of the La 2 O 3 component is preferably 45.0%, more preferably 40.0%, more preferably 38.0%, and still more preferably 37.0%. As the La 2 O 3 component, La 2 O 3 , La(NO 3 ) 3 ·XH 2 O (X is an arbitrary integer), etc. can be used as raw materials.
TiO 2成分為其含量大於0%時,能夠提高玻璃的折射率,調低阿貝數,提高部分色散比,且能夠提高耐失透性的必須成分。因此,TiO 2成分的含量,其下限以大於0%為佳,較佳是5.0%,更佳是10.0%,進而較佳是15.0%,進而更佳是18.0%,再進而更佳是大於20.0%。 另一方面,藉由將TiO 2成分的含量設為45.0%以下,可減少玻璃的著色並提高可見光穿透率。此外,亦能夠抑制因含有過剩的TiO 2成分而引起的失透。因此,TiO 2成分的含量,其上限以45.0%為佳,較佳是38.0%,更佳是32.0%,進而更佳是27.0%,再進而更佳是25.0%。 TiO 2成分,可使用TiO 2等作為原料。 When the content of the TiO 2 component is greater than 0%, it is an essential component that can increase the refractive index of the glass, lower the Abbe number, increase the partial dispersion ratio, and improve the devitrification resistance. Therefore, the lower limit of the content of the TiO 2 component is preferably greater than 0%, preferably 5.0%, more preferably 10.0%, further preferably 15.0%, still more preferably 18.0%, and still more preferably greater than 20.0 %. On the other hand, by setting the content of the TiO 2 component to 45.0% or less, the coloring of the glass can be reduced and the visible light transmittance can be improved. In addition, devitrification caused by excessive TiO 2 component content can also be suppressed. Therefore, the upper limit of the content of the TiO 2 component is preferably 45.0%, more preferably 38.0%, more preferably 32.0%, still more preferably 27.0%, still more preferably 25.0%. TiO 2 component, TiO 2 etc. can be used as raw materials.
BaO成分為其含量大於0%時,能夠提高玻璃的折射率或耐失透性,且能夠提高玻璃原料的熔融性的必須成分。因此,BaO成分的含量,其下限以大於0%為佳,較佳是5.0%,更佳是8.0%,進而更佳是10.0%。 另一方面,藉由將BaO成分的含量設為40.0%以下,不易降低玻璃的折射率,且能夠減少玻璃的失透。因此,BaO成分的含量,其上限以40.0%為佳,較佳是35.0%,更佳是28.0%,進而更佳是23.0%,再進而更佳是20.0%。 BaO成分,可使用BaCO 3、Ba(NO 3) 2等作為原料。 The BaO component is an essential component that can improve the refractive index or devitrification resistance of the glass and improve the meltability of the glass raw material when the content exceeds 0%. Therefore, the lower limit of the content of the BaO component is preferably greater than 0%, preferably 5.0%, more preferably 8.0%, and still more preferably 10.0%. On the other hand, by setting the content of the BaO component to 40.0% or less, the refractive index of the glass is less likely to decrease and the devitrification of the glass can be reduced. Therefore, the upper limit of the content of the BaO component is preferably 40.0%, more preferably 35.0%, more preferably 28.0%, still more preferably 23.0%, still more preferably 20.0%. As the BaO component, BaCO 3 , Ba(NO 3 ) 2 , etc. can be used as raw materials.
B 2O 3成分與SiO 2成分的含量之和(質量和),較佳是5.0%以上,30.0%以下。 特別是,藉由將該和設為5.0%以上,可抑制因B 2O 3成分或SiO 2成分的不足而引起的耐失透性低下。因此,質量和(B 2O 3+SiO 2),其下限以5.0%為佳,較佳是7.0%,更佳是9.0%。 另一方面,藉由將該和設為30.0%以下,能夠抑制因含有過剩的該等成分而引起的折射率低下,故能夠輕易獲得所期望的高折射率。因此,質量和(B 2O 3+SiO 2),其上限以30.0%為佳,較佳是23.0%,更佳是18.0%,進而更佳是16.50%。 The total content (mass sum) of the B 2 O 3 component and the SiO 2 component is preferably 5.0% or more and 30.0% or less. In particular, by setting the sum to 5.0% or more, it is possible to suppress a decrease in devitrification resistance due to insufficient B 2 O 3 components or SiO 2 components. Therefore, the lower limit of the mass sum (B 2 O 3 +SiO 2 ) is preferably 5.0%, more preferably 7.0%, and more preferably 9.0%. On the other hand, by setting the sum to 30.0% or less, a decrease in the refractive index caused by excessive inclusion of these components can be suppressed, so that a desired high refractive index can be easily obtained. Therefore, the upper limit of the mass sum (B 2 O 3 +SiO 2 ) is preferably 30.0%, more preferably 23.0%, more preferably 18.0%, and still more preferably 16.50%.
在此,TiO 2成分的含量與TiO 2成分及BaO成分的含量之和的比率(質量比),以0.10以上為佳。藉此,除了能夠維持高折射率與高色散之外,亦能夠獲得高部分色散比。因此,質量比TiO 2/(TiO 2+BaO),其下限以0.10為佳,較佳是0.30,更佳是0.40,進而更佳是0.45。 另一方面,藉由將該質量比設為0.90以下,可減少玻璃的著色並提高可見光穿透率,且能夠抑制失透。因此,質量比TiO 2/(TiO 2+BaO),其上限以0.90為佳,較佳是0.80,更佳是0.73,進而更佳是0.68。 Here, the ratio (mass ratio) between the content of the TiO 2 component and the sum of the contents of the TiO 2 component and BaO component (mass ratio) is preferably 0.10 or more. In this way, in addition to maintaining a high refractive index and high dispersion, a high partial dispersion ratio can also be obtained. Therefore, the lower limit of the mass ratio TiO 2 /(TiO 2 +BaO) is preferably 0.10, more preferably 0.30, more preferably 0.40, and still more preferably 0.45. On the other hand, by setting the mass ratio to 0.90 or less, the coloring of the glass can be reduced, the visible light transmittance can be improved, and devitrification can be suppressed. Therefore, the upper limit of the mass ratio TiO 2 /(TiO 2 +BaO) is preferably 0.90, more preferably 0.80, more preferably 0.73, and even more preferably 0.68.
SiO 2成分為其含量大於0%時,能夠提高耐失透性的任意成分。因此,SiO 2成分的含量,其下限以大於0%為佳,較佳是大於0.5%,更佳是大於1.0%,進而更佳是大於2.0%。 另一方面,藉由將SiO 2成分的含量設為30.0%以下,可使SiO 2成分在熔融玻璃中容易熔融,免去以高溫進行熔解。SiO 2成分的含量,其上限以30.0%為佳,較佳是23.0%,更佳是16.0%,進而更佳是11.0%,再進而更佳是9.0%。 SiO 2成分,可使用SiO 2、K 2SiF 6、Na 2SiF 6等作為原料。 The SiO 2 component is any component that can improve the devitrification resistance when its content is greater than 0%. Therefore, the lower limit of the content of the SiO 2 component is preferably greater than 0%, preferably greater than 0.5%, more preferably greater than 1.0%, and still more preferably greater than 2.0%. On the other hand, by setting the content of the SiO 2 component to 30.0% or less, the SiO 2 component can be easily melted in the molten glass, thereby eliminating the need for melting at high temperatures. The upper limit of the content of the SiO 2 component is preferably 30.0%, more preferably 23.0%, more preferably 16.0%, still more preferably 11.0%, still more preferably 9.0%. As the SiO 2 component, SiO 2 , K 2 SiF 6 , Na 2 SiF 6 , etc. can be used as raw materials.
B 2O 3成分為其含量大於0%時,能夠在玻璃的內部形成網狀結構,促進安定的玻璃形成,提高耐失透性的任意成分。因此,B 2O 3成分的含量,其下限以大於0%為佳,較佳是大於0.5%,更佳是大於1.0%,進而更佳是大於2.0%。 另一方面,藉由將B 2O 3成分的含量設為30.0%以下,能夠抑制折射率的低下,可使阿貝數變小,且能夠抑制化學耐久性的惡化。因此,B 2O 3成分的含量,其上限以30.0%以下為佳,較佳是20.0%,更佳是低於15.0%,進而更佳是12.0%,再進而更佳是低於10.0%。 B 2O 3成分,可使用H 3BO 3、Na 2B 4O 7、Na 2B 4O 7・10H 2O、BPO 4等作為原料。 The B 2 O 3 component is any component that, when the content exceeds 0%, can form a network structure inside the glass, promote the formation of stable glass, and improve the devitrification resistance. Therefore, the lower limit of the content of the B 2 O 3 component is preferably greater than 0%, more preferably greater than 0.5%, more preferably greater than 1.0%, still more preferably greater than 2.0%. On the other hand, by setting the content of the B 2 O 3 component to 30.0% or less, a decrease in the refractive index can be suppressed, the Abbe number can be reduced, and deterioration of chemical durability can be suppressed. Therefore, the upper limit of the content of the B 2 O 3 component is preferably 30.0% or less, more preferably 20.0%, more preferably less than 15.0%, still more preferably 12.0%, still more preferably less than 10.0%. As the B 2 O 3 component, H 3 BO 3 , Na 2 B 4 O 7 , Na 2 B 4 O 7・10H 2 O, BPO 4 , etc. can be used as raw materials.
ZnO成分為其含量大於0%時,能夠改善玻璃的熔融性,並能夠降低玻璃轉移點,且可減少失透的任意成分。因此,ZnO成分的含量,其下限以大於0%為佳,較佳是大於0.5%,更佳是大於1.0%,進而更佳是大於1.5%。 另一方面,藉由將ZnO成分的含量設為20.0%以下,能夠降低折射率的低下或失透。此外,由於藉此可提高熔融玻璃的黏性,而能夠減少玻璃的條紋發生。因此,ZnO成分的含量,其上限以20.0%為佳,較佳是15.0%,更佳是11.0%,進而更佳是8.0%。 ZnO成分,可使用ZnO、ZnF 2等作為原料。 The ZnO component is any component that can improve the meltability of glass, lower the glass transition point, and reduce devitrification when its content is greater than 0%. Therefore, the lower limit of the content of the ZnO component is preferably greater than 0%, preferably greater than 0.5%, more preferably greater than 1.0%, and still more preferably greater than 1.5%. On the other hand, by setting the content of the ZnO component to 20.0% or less, reduction in the refractive index and devitrification can be reduced. In addition, since the viscosity of the molten glass can be increased, the occurrence of streaks in the glass can be reduced. Therefore, the upper limit of the content of the ZnO component is preferably 20.0%, more preferably 15.0%, more preferably 11.0%, and still more preferably 8.0%. ZnO component, ZnO, ZnF 2 , etc. can be used as raw materials.
Y 2O 3成分為其含量大於0%時,可抑制玻璃的材料成本上升的任意成分。 藉由將Y 2O 3成分的含量設為15.0%以下,能夠抑制玻璃的折射率低下,可使阿貝數變小,且能夠提高玻璃的耐失透性。因此,Y 2O 3成分的含量,其上限以15.0%為佳,較佳是10.0%,更佳是5.0%。 Y 2O 3成分,可使用Y 2O 3、YF 3等作為原料。 The Y 2 O 3 component is any component that can suppress an increase in the material cost of glass when the content exceeds 0%. By setting the content of the Y 2 O 3 component to 15.0% or less, a decrease in the refractive index of the glass can be suppressed, the Abbe number can be reduced, and the devitrification resistance of the glass can be improved. Therefore, the upper limit of the Y 2 O 3 component content is preferably 15.0%, more preferably 10.0%, and more preferably 5.0%. Y 2 O 3 component, Y 2 O 3 , YF 3 , etc. can be used as raw materials.
Nb 2O 5成分為其含量大於0%時,能夠提高玻璃的折射率,且能夠提高耐失透性的任意成分。因此,Nb 2O 5成分的含量,其下限以大於0%為佳,較佳是2.0%,更佳是4.0%。 另一方面,藉由將Nb 2O 5成分的含量設為25.0%以下,能夠抑制因含有過剩的Nb 2O 5而引起的玻璃耐失透性低下,或是能夠抑制可見光的穿透率低下,且可抑制玻璃的材料成本上升。因此,Nb 2O 5成分的含量,其上限以25.0%為佳,較佳是20.0%,更佳是16.0%,進而更佳是13.0%。 Nb 2O 5成分,可使用Nb 2O 5等作為原料。 The Nb 2 O 5 component is any component that can increase the refractive index of glass and improve the devitrification resistance when its content exceeds 0%. Therefore, the lower limit of the content of the Nb 2 O 5 component is preferably greater than 0%, preferably 2.0%, and more preferably 4.0%. On the other hand, by setting the content of the Nb 2 O 5 component to 25.0% or less, it is possible to suppress a decrease in the devitrification resistance of the glass caused by excessive Nb 2 O 5 content, or to suppress a decrease in the transmittance of visible light. , and can suppress the increase in the material cost of glass. Therefore, the upper limit of the content of the Nb 2 O 5 component is preferably 25.0%, more preferably 20.0%, more preferably 16.0%, and still more preferably 13.0%. Nb 2 O 5 component, Nb 2 O 5 , etc. can be used as raw materials.
Yb 2O 3成分為其含量大於0%時,可提高玻璃的折射率的任意成分。 另一方面,藉由將Yb 2O 3成分的含量設為15.0%以下,能夠提高玻璃的耐失透性,且可使阿貝數變小。因此,Yb 2O 3成分的含量,其上限以15.0%為佳,較佳是10.0%,更佳是5.0%。 Yb 2O 3成分,可使用Yb 2O 3等作為原料。 The Yb 2 O 3 component is any component that can increase the refractive index of glass when its content is greater than 0%. On the other hand, by setting the content of the Yb 2 O 3 component to 15.0% or less, the devitrification resistance of the glass can be improved and the Abbe number can be reduced. Therefore, the upper limit of the content of the Yb 2 O 3 component is preferably 15.0%, more preferably 10.0%, and more preferably 5.0%. Yb 2 O 3 component, Yb 2 O 3 , etc. can be used as raw materials.
Gd 2O 3成分為其含量大於0%時,可提高玻璃的折射率,且能夠提高阿貝數的任意成分。 另一方面,藉由將稀土類元素中特別高價的Gd 2O 3成分降低至15.0%以下,可降低玻璃的材料成本,故能夠製作出價格更加低廉的光學玻璃。此外,藉此能夠使玻璃的阿貝數不至於上升至大於所需。因此,Gd 2O 3成分的含量,其上限以15.0%為佳,較佳是10.0%,更佳是5.0%。 Gd 2O 3成分,可使用Gd 2O 3、GdF 3等作為原料。 The Gd 2 O 3 component is any component that can increase the refractive index of glass and increase the Abbe number when the content exceeds 0%. On the other hand, by reducing the Gd 2 O 3 component, which is particularly expensive among rare earth elements, to less than 15.0%, the material cost of the glass can be reduced, and therefore more affordable optical glass can be produced. In addition, this can prevent the Abbe number of the glass from rising higher than necessary. Therefore, the upper limit of the content of the Gd 2 O 3 component is preferably 15.0%, more preferably 10.0%, and more preferably 5.0%. Gd 2 O 3 component, Gd 2 O 3 , GdF 3 , etc. can be used as raw materials.
此外,本發明的光學玻璃中,La 2O 3成分、Nb 2O 5成分、Gd 2O 3成分、及Yb 2O 3成分的含量之和(質量和),以60.0%以下為佳。藉此,能夠降低該等高價成分的含量,故能夠抑制玻璃的材料成本,且可使阿貝數變小。因此,質量和(La 2O 3+Nb 2O 5+Gd 2O 3+Yb 2O 3),其上限以60.0%為佳,較佳是57.0%,更佳是53.0%,進而更佳是49.0%,再進而更佳是47.0%。 另一方面,藉由含有大於0%的該等成分的質量和,可獲得所期望的高折射率。因此,其下限以大於0%為佳,較佳是10.0%,更佳是20.0%,更較佳是25.0%,進而更佳是30.0%,再進而更佳是35.0%。 In addition, in the optical glass of the present invention, the total content (mass sum) of the La 2 O 3 component, the Nb 2 O 5 component, the Gd 2 O 3 component, and the Yb 2 O 3 component is preferably 60.0% or less. Thereby, the content of these expensive components can be reduced, so the material cost of the glass can be suppressed and the Abbe number can be reduced. Therefore, the upper limit of the mass sum (La 2 O 3 +Nb 2 O 5 +Gd 2 O 3 +Yb 2 O 3 ) is preferably 60.0%, more preferably 57.0%, more preferably 53.0%, and still more preferably 49.0%, and even better is 47.0%. On the other hand, by containing more than 0% of the mass sum of these components, the desired high refractive index can be obtained. Therefore, the lower limit is preferably greater than 0%, preferably 10.0%, more preferably 20.0%, still more preferably 25.0%, still more preferably 30.0%, still more preferably 35.0%.
Ln 2O 3成分(式中,Ln是選自La、Gd、Y、Yb所成群組中的1種以上)的含量之和(質量和),以大於0%至50%為佳。 特別是,藉由將該質量和設為大於0%,可提高玻璃的折射率,因此能夠輕易獲得高折射率的玻璃。此外,藉此可減少玻璃的著色。因此,Ln 2O 3成分的含量之質量和,其下限以大於0%為佳,較佳是1.0%,更佳是3.0%,進而更佳是5.0%。 另一方面,藉由將該質量和設為50.0%以下,可提高耐失透性,且可使阿貝數變小。因此,Ln 2O 3成分的含量之質量和,其上限以50.0%為佳,較佳是低於40.0%,更佳是30.0%,進而更佳是25.0%。 The sum of the contents (mass sum) of the Ln 2 O 3 component (in the formula, Ln is one or more selected from the group consisting of La, Gd, Y, and Yb) is preferably greater than 0% to 50%. In particular, by setting the mass sum to be greater than 0%, the refractive index of the glass can be increased, so that glass with a high refractive index can be easily obtained. In addition, the staining of the glass can be reduced. Therefore, the lower limit of the mass sum of the content of the Ln 2 O 3 component is preferably greater than 0%, more preferably 1.0%, more preferably 3.0%, and still more preferably 5.0%. On the other hand, by setting the mass sum to 50.0% or less, the devitrification resistance can be improved and the Abbe number can be reduced. Therefore, the upper limit of the mass sum of the content of the Ln 2 O 3 component is preferably 50.0%, more preferably less than 40.0%, more preferably 30.0%, and still more preferably 25.0%.
在此,TiO 2成分的含量與La 2O 3成分、Nb 2O 5成分、Gd 2O 3成分、及Yb 2O 3成分的含量之和的比率(質量比),以大於0為佳。藉此,除了能夠維持高折射率與高色散之外,亦能夠獲得高部分色散比,且可使生產成本低廉。因此,質量比TiO 2/(La 2O 3+Nb 2O 5+Gd 2O 3+Yb 2O 3),其下限以大於0為佳,較佳是0.10,更佳是0.20,進而更佳是0.40。 另一方面,藉由將該質量比設為2.00以下,可減少玻璃的著色並提高可見光穿透率,且能夠抑制失透。因此,質量比TiO 2/(La 2O 3+Nb 2O 5+Gd 2O 3+Yb 2O 3),其上限以2.00為佳,較佳是1.00,更佳是0.80,進而更佳是0.66。 Here, the ratio (mass ratio) of the content of the TiO 2 component to the sum of the contents of the La 2 O 3 component, Nb 2 O 5 component, Gd 2 O 3 component, and Yb 2 O 3 component is preferably greater than 0. In this way, in addition to maintaining a high refractive index and high dispersion, a high partial dispersion ratio can also be obtained, and the production cost can be reduced. Therefore, the lower limit of the mass ratio TiO 2 /(La 2 O 3 +Nb 2 O 5 +Gd 2 O 3 +Yb 2 O 3 ) is preferably greater than 0, preferably 0.10, more preferably 0.20, and even better It's 0.40. On the other hand, by setting the mass ratio to 2.00 or less, the coloring of the glass can be reduced, the visible light transmittance can be improved, and devitrification can be suppressed. Therefore, the upper limit of the mass ratio TiO 2 /(La 2 O 3 +Nb 2 O 5 +Gd 2 O 3 +Yb 2 O 3 ) is preferably 2.00, more preferably 1.00, more preferably 0.80, and even more preferably 0.66.
在此,TiO 2成分的含量與BaO成分的含量的比率(質量比),以大於0為佳。藉此,除了能夠維持高折射率與高色散之外,亦能夠獲得高部分色散比。質量比TiO 2/BaO,其下限以大於0為佳,較佳是0.10,更佳是0.40,進而更佳是0.60。 另一方面,藉由將該質量比設為3.00以下,可減少玻璃的著色並提高可見光穿透率,且能夠抑制失透。因此,質量比TiO 2/BaO,其上限以3.00為佳,較佳是2.00,更佳是1.60。 Here, the ratio (mass ratio) of the content of the TiO 2 component to the content of the BaO component is preferably greater than 0. In this way, in addition to maintaining a high refractive index and high dispersion, a high partial dispersion ratio can also be obtained. The lower limit of the mass ratio TiO 2 /BaO is preferably greater than 0, more preferably 0.10, more preferably 0.40, still more preferably 0.60. On the other hand, by setting the mass ratio to 3.00 or less, the coloring of the glass can be reduced, the visible light transmittance can be improved, and devitrification can be suppressed. Therefore, the upper limit of the mass ratio TiO 2 /BaO is preferably 3.00, more preferably 2.00, and more preferably 1.60.
在此,TiO 2成分與WO 3成分的含量之和與BaO成分的比率(質量比),以大於0為佳。藉此,除了能夠維持高折射率與高色散之外,亦能夠獲得高部分色散比,且能夠提高耐失透性。因此,質量比(TiO 2+WO 3)/BaO,其下限以大於0為佳,較佳是0.30,更佳是0.60,進而更佳是0.80,再進而更佳是1.00。 另一方面,藉由將該質量比設為3.00以下,可減少玻璃的著色並提高可見光穿透率,且能夠抑制失透。因此,質量比(TiO 2+WO 3)/BaO,其上限以3.00為佳,較佳是2.50,更佳是1.90。 Here, the ratio (mass ratio) of the sum of the contents of the TiO 2 component and the WO 3 component to the BaO component is preferably greater than 0. In this way, in addition to maintaining a high refractive index and high dispersion, a high partial dispersion ratio can also be obtained, and the devitrification resistance can be improved. Therefore, the lower limit of the mass ratio (TiO 2 +WO 3 )/BaO is preferably greater than 0, preferably 0.30, more preferably 0.60, still more preferably 0.80, still more preferably 1.00. On the other hand, by setting the mass ratio to 3.00 or less, the coloring of the glass can be reduced, the visible light transmittance can be improved, and devitrification can be suppressed. Therefore, the upper limit of the mass ratio (TiO 2 +WO 3 )/BaO is preferably 3.00, more preferably 2.50, and more preferably 1.90.
TiO 2成分與Nb 2O 5成分的含量之和(質量和),以大於0%為佳。藉此,能夠提高玻璃的折射率/色散,且可提高耐失透性。因此,質量和(TiO 2+Nb 2O 5),其下限以大於0%為佳,較佳是大於10.0%,更佳是大於15.0%,進而更佳是大於20.0%,再進而更佳是大於25.0%。 另一方面,藉由將該質量和設為60.0%以下,可減少玻璃的著色並提高可見光穿透率,且能夠抑制失透。因此,質量和(TiO 2+Nb 2O 5),其上限以60.0%為佳,較佳是低於50.0%,更佳是45.0%,更較佳是40.0%,進而更佳是35.0%,再進而更佳是33.0%。 The total content (mass sum) of the TiO 2 component and the Nb 2 O 5 component is preferably greater than 0%. This can increase the refractive index/dispersion of the glass and improve the devitrification resistance. Therefore, the lower limit of the mass sum (TiO 2 +Nb 2 O 5 ) is preferably greater than 0%, preferably greater than 10.0%, more preferably greater than 15.0%, still more preferably greater than 20.0%, still more preferably greater than 25.0%. On the other hand, by setting the mass sum to 60.0% or less, the coloring of the glass can be reduced, the visible light transmittance can be improved, and devitrification can be suppressed. Therefore, the upper limit of the mass sum (TiO 2 +Nb 2 O 5 ) is preferably 60.0%, preferably less than 50.0%, more preferably 45.0%, more preferably 40.0%, and still more preferably 35.0%, Even better is 33.0%.
Rn 2O成分(式中,Rn是選自Li、Na、K、Cs所成群組中的1種以上)的合計量,以15.0%以下為佳。藉此,能夠抑制玻璃的折射率低下,且能夠提高耐失透性。因此,Rn 2O成分的質量和,其上限以15.0%為佳,較佳是10.0%,更佳是低於5.0%,進而更佳是低於1.0%。 The total amount of the Rn 2 O component (in the formula, Rn is one or more selected from the group consisting of Li, Na, K, and Cs) is preferably 15.0% or less. Thereby, it is possible to suppress a decrease in the refractive index of the glass and improve the devitrification resistance. Therefore, the upper limit of the mass sum of the Rn 2 O component is preferably 15.0%, more preferably 10.0%, more preferably less than 5.0%, still more preferably less than 1.0%.
RO成分(式中,R是選自Mg、Ca、Sr、Ba所成群組中的1種以上)的含量之和(質量和),以35.0%以下為佳。藉此能夠減少因含有過剩的RO成分而引起的失透,且可抑制折射率低下。因此,RO成分的含量的質量和,其上限以35.0%為佳,較佳是30.0%,更佳是27.0%,進而更佳是低於23.0%,再進而更佳是20.0%。 另一方面,藉由將該質量和設為大於0%,可提高玻璃原料的熔融性或玻璃的安定性。因此,RO成分的合計含量,其下限以大於0%為佳,較佳是4.0%,更佳是7.0%,進而更佳是大於9.0%。 The total content (mass sum) of the RO components (in the formula, R is one or more selected from the group consisting of Mg, Ca, Sr, and Ba) is preferably 35.0% or less. This can reduce devitrification caused by excessive RO component content and suppress a decrease in the refractive index. Therefore, the upper limit of the mass sum of the RO component content is preferably 35.0%, more preferably 30.0%, more preferably 27.0%, more preferably less than 23.0%, and still more preferably 20.0%. On the other hand, by setting the mass sum to be greater than 0%, the meltability of the glass raw material or the stability of the glass can be improved. Therefore, the lower limit of the total content of RO components is preferably greater than 0%, more preferably 4.0%, more preferably 7.0%, and still more preferably greater than 9.0%.
ZrO 2成分為其含量大於0%時,有助於玻璃的高折射率化及低色散化,且能夠提高玻璃的耐失透性的任意成分。因此,ZrO 2成分的含量,其下限以大於0%為佳,較佳是0.5%,更佳是1.0%。 另一方面,藉由將ZrO 2成分設為20.0%以下,能夠抑制因含有過剩的ZrO 2成分而引起的玻璃耐失透性低下或阿貝數上升至大於所需的程度。因此,ZrO 2成分的含量,其上限以20.0%為佳,較佳是16.0%,更佳是12.0%,進而更佳是9.0%,再進而更佳是低於6.5%。 ZrO 2成分,可使用ZrO 2、ZrF 4等作為原料。 The ZrO 2 component is any component that contributes to high refractive index and low dispersion of glass and can improve the devitrification resistance of glass when its content exceeds 0%. Therefore, the lower limit of the content of the ZrO 2 component is preferably greater than 0%, preferably 0.5%, and more preferably 1.0%. On the other hand, by setting the ZrO 2 component to 20.0% or less, it is possible to suppress a decrease in the devitrification resistance of the glass or an increase in the Abbe's number from being higher than necessary due to the excessive ZrO 2 component content. Therefore, the upper limit of the content of the ZrO 2 component is preferably 20.0%, more preferably 16.0%, more preferably 12.0%, still more preferably 9.0%, and still more preferably less than 6.5%. As a ZrO 2 component, ZrO 2 , ZrF 4 , etc. can be used as raw materials.
WO 3成分為其含量大於0%時,除了可減少因其他高折射率成分所造成的玻璃著色之外,亦能夠提高折射率,並提高部分色散比,且可提高玻璃的耐失透性的任意成分。此外,WO 3成分亦是能夠降低玻璃轉移點的成分。因此,WO 3成分的含量,其下限以大於0%為佳,較佳是0.1%,更佳是0.2%,進而更佳是0.3%。 另一方面,藉由將WO 3成分的含量設為10.0%以下,可減少因WO 3成分所造成的玻璃著色,而提高可見光穿透率。因此,WO 3成分的含量,其上限以10.0%為佳,較佳是5.0%,更佳是3.0%。 WO 3成分,可使用WO 3等作為原料。 When the content of the WO 3 component is greater than 0%, in addition to reducing the coloring of the glass caused by other high refractive index components, it can also increase the refractive index, increase the partial dispersion ratio, and improve the devitrification resistance of the glass. Any ingredients. In addition, the WO 3 component is also a component that can lower the glass transition point. Therefore, the lower limit of the content of the WO 3 component is preferably greater than 0%, preferably 0.1%, more preferably 0.2%, and still more preferably 0.3%. On the other hand, by setting the content of the WO 3 component to 10.0% or less, glass coloring caused by the WO 3 component can be reduced and the visible light transmittance can be improved. Therefore, the upper limit of the content of the WO 3 component is preferably 10.0%, more preferably 5.0%, and more preferably 3.0%. As the WO 3 component, WO 3 and the like can be used as raw materials.
Ta 2O 5成分為其含量大於0%時,能夠提高玻璃的折射率,且可提高耐失透性的任意成分。 另一方面,藉由將高價的Ta 2O 5成分降低至10.0%以下,可降低玻璃的材料成本,故能夠製作出價格更加低廉的光學玻璃。此外,藉由將Ta 2O 5成分的含量設為10.0%以下,可使原料的熔解溫度變低,減少原料熔解所需的能量,因此亦能夠降低光學玻璃的製造成本。因此,Ta 2O 5成分的含量,其上限以10.0%為佳,較佳是8.0%,更佳是5.0%。特別是由製作價格更加低廉的光學玻璃之觀點而言,Ta 2O 5成分的含量,其上限以4.0%為佳,更佳是3.0%,進而更佳是低於1.0%,最佳是不含有。 Ta 2O 5成分,可使用Ta 2O 5等作為原料。 The Ta 2 O 5 component is any component that can increase the refractive index of the glass and improve the devitrification resistance when the content is greater than 0%. On the other hand, by reducing the expensive Ta 2 O 5 component to less than 10.0%, the material cost of the glass can be reduced, and therefore more affordable optical glass can be produced. In addition, by setting the content of the Ta 2 O 5 component to 10.0% or less, the melting temperature of the raw material can be lowered and the energy required for melting the raw material can be reduced. Therefore, the manufacturing cost of optical glass can also be reduced. Therefore, the upper limit of the content of the Ta 2 O 5 component is preferably 10.0%, more preferably 8.0%, and more preferably 5.0%. Especially from the viewpoint of producing cheaper optical glass, the upper limit of the content of the Ta 2 O 5 component is preferably 4.0%, more preferably 3.0%, further preferably less than 1.0%, and most preferably no contain. Ta 2 O 5 component, Ta 2 O 5 , etc. can be used as raw materials.
MgO成分為其含量大於0%時,可提高玻璃原料的熔融性或玻璃的耐失透性的任意成分。 另一方面,藉由將MgO成分的含量設為15.0%以下,能夠抑制因含有過剩的該等成分而引起的折射率低下或耐失透性低下。因此,MgO成分的含量,其上限以15.0%為佳,較佳是10.0%,更佳是5.0%。 MgO成分,可使用MgCO 3、MgF 2等作為原料。 The MgO component is any component that can improve the meltability of the glass raw material or the devitrification resistance of the glass when its content exceeds 0%. On the other hand, by setting the content of the MgO component to 15.0% or less, it is possible to suppress a decrease in the refractive index or a decrease in devitrification resistance caused by excessive inclusion of these components. Therefore, the upper limit of the content of the MgO component is preferably 15.0%, more preferably 10.0%, and more preferably 5.0%. For the MgO component, MgCO 3 , MgF 2 , etc. can be used as raw materials.
CaO成分為其含量大於0%時,可提高玻璃的折射率或耐失透性,且能夠提高玻璃原料的熔融性的任意成分。因此CaO成分的含量,其下限以大於0%為佳,較佳是0.5%,更佳是1.5%,進而更佳是3.0%。 另一方面,藉由將CaO成分的含量設為15.0%以下,不易降低玻璃的折射率,且能夠減少玻璃的失透。因此,CaO成分的含量,其上限以15.0%為佳,較佳是10.0%,更佳是5.0%。 CaO成分,可使用CaCO 3、CaF 2等作為原料。 The CaO component is any component that can improve the refractive index or devitrification resistance of the glass and improve the meltability of the glass raw material when the content exceeds 0%. Therefore, the lower limit of the content of the CaO component is preferably greater than 0%, preferably 0.5%, more preferably 1.5%, and still more preferably 3.0%. On the other hand, by setting the content of the CaO component to 15.0% or less, the refractive index of the glass is less likely to decrease and the devitrification of the glass can be reduced. Therefore, the upper limit of the content of the CaO component is preferably 15.0%, more preferably 10.0%, and more preferably 5.0%. As a CaO component, CaCO 3 , CaF 2 , etc. can be used as raw materials.
SrO成分為其含量大於0%時,可提高玻璃的折射率或耐失透性,且能夠提高玻璃原料的熔融性的任意成分。因此SrO成分的含量,其下限以大於0%為佳,較佳是0.5%,更佳是1.5%,進而更佳是3.0%。 另一方面,藉由將SrO成分的含量設為15.0%以下,不易降低玻璃的折射率,且能夠減少玻璃的失透。因此,SrO成分的含量,其上限以15.0%為佳,較佳是10.0%,更佳是5.0%。 SrO成分,可使用SrCO 3、SrF 2作為原料。 The SrO component is any component that can improve the refractive index or devitrification resistance of the glass and improve the meltability of the glass raw material when the content is greater than 0%. Therefore, the lower limit of the content of the SrO component is preferably greater than 0%, preferably 0.5%, more preferably 1.5%, and still more preferably 3.0%. On the other hand, by setting the content of the SrO component to 15.0% or less, the refractive index of the glass is less likely to decrease and the devitrification of the glass can be reduced. Therefore, the upper limit of the SrO component content is preferably 15.0%, more preferably 10.0%, and more preferably 5.0%. As the SrO component, SrCO 3 and SrF 2 can be used as raw materials.
Li 2O成分、Na 2O成分、及K 2O成分為其中至少任一者的含量大於0%時,能夠改善玻璃的熔融性的任意成分。尤其K 2O成分亦是能夠更加提高玻璃的部分色散比之成分。 另一方面,藉由減少Li 2O成分、Na 2O成分或K 2O成分的含量,可抑制玻璃的折射率低下,且能夠減少失透。特別是藉由減少Li 2O成分的含量,可抑制玻璃的部分色散比低下。因此,Li 2O成分、Na 2O成分及K 2O成分之中至少任一者的含量,以15.0%以下為佳,較佳是低於10.0%,更佳是低於5.0%,進而更佳是低於1.0%。 Li 2O成分、Na 2O成分及K 2O成分,可使用Li 2CO 3、LiNO 3、LiF、Na 2CO 3、NaNO 3、NaF、Na 2SiF 6、K 2CO 3、KNO 3、KF、KHF 2、K 2SiF 6等作為原料。 The Li 2 O component, the Na 2 O component, and the K 2 O component are any components that can improve the meltability of the glass when the content of at least any one of them exceeds 0%. In particular, the K 2 O component is also a component that can further increase the partial dispersion ratio of glass. On the other hand, by reducing the content of the Li 2 O component, the Na 2 O component, or the K 2 O component, a decrease in the refractive index of the glass can be suppressed and devitrification can be reduced. In particular, by reducing the content of the Li 2 O component, a decrease in the partial dispersion ratio of the glass can be suppressed. Therefore, the content of at least one of the Li 2 O component, the Na 2 O component and the K 2 O component is preferably 15.0% or less, more preferably less than 10.0%, more preferably less than 5.0%, and more preferably Preferably it is less than 1.0%. As the Li 2 O component, Na 2 O component and K 2 O component, Li 2 CO 3 , LiNO 3 , LiF, Na 2 CO 3 , NaNO 3 , NaF, Na 2 SiF 6 , K 2 CO 3 , KNO 3 , can be used. KF, KHF 2 , K 2 SiF 6 , etc. are used as raw materials.
P 2O 5成分為其含量大於0%時,可提高玻璃耐失透性的任意成分。尤其藉由將P 2O 5成分的含量設為10.0%以下,能夠抑制玻璃的化學耐久性的低下,特別是耐水性的低下。因此,P 2O 5成分的含量,其上限以10.0%為佳,較佳是5.0%,更佳是3.0%。 P 2O 5成分,可使用Al(PO 3) 3、Ca(PO 3) 2、Ba(PO 3) 2、BPO 4、H 3PO 4等作為原料。 The P 2 O 5 component is any component that can improve the devitrification resistance of glass when its content is greater than 0%. In particular, by setting the content of the P 2 O 5 component to 10.0% or less, it is possible to suppress a decrease in the chemical durability of the glass, especially a decrease in the water resistance. Therefore, the upper limit of the content of the P 2 O 5 component is preferably 10.0%, more preferably 5.0%, and more preferably 3.0%. As the P 2 O 5 component, Al(PO 3 ) 3 , Ca(PO 3 ) 2 , Ba(PO 3 ) 2 , BPO 4 , H 3 PO 4 , etc. can be used as raw materials.
GeO 2成分為其含量大於0%時,可提高玻璃的折射率,且能夠提高耐失透性的任意成分。然而,由於GeO 2的原料價格昂貴,若使用量大會造成材料成本變高,而有損藉由減少Gd 2O 3成分或Ta 2O 5成分所帶來的成本下降效果。因此,GeO 2成分的含量,其上限以10.0%為佳,較佳是5.0%,更佳是1.0%,最佳是不含有。 GeO 2成分,可使用GeO 2等作為原料。 The GeO 2 component is any component that can increase the refractive index of glass and improve the devitrification resistance when the content is greater than 0%. However, since the raw material of GeO 2 is expensive, if it is used in large amounts, the material cost will increase, which will undermine the cost reduction effect brought about by reducing the Gd 2 O 3 component or Ta 2 O 5 component. Therefore, the upper limit of the content of the GeO 2 component is preferably 10.0%, more preferably 5.0%, more preferably 1.0%, and most preferably none. GeO 2 component, GeO 2 etc. can be used as raw materials.
Al 2O 3成分與Ga 2O 3成分為其含量大於0%時,可提高玻璃的化學耐久性,且能夠提高玻璃的耐失透性的任意成分。 另一方面,藉由將Al 2O 3成分與Ga 2O 3成分的含量分別設為15.0%以下,能夠抑制因含有過剩的該等成分而引起的玻璃耐失透性低下。因此,Al 2O 3成分與Ga 2O 3成分各別的含量,其上限以15.0%為佳,較佳是8.0%,更佳是3.0%。 Al 2O 3成分與Ga 2O 3成分,可使用Al 2O 3、Al(OH) 3、AlF 3、Ga 2O 3、Ga(OH) 3等作為原料。 The Al 2 O 3 component and the Ga 2 O 3 component are any components that can improve the chemical durability of the glass and improve the devitrification resistance of the glass when the content exceeds 0%. On the other hand, by setting the content of each of the Al 2 O 3 component and the Ga 2 O 3 component to 15.0% or less, it is possible to suppress a decrease in the devitrification resistance of the glass caused by excessive inclusion of these components. Therefore, the upper limit of the respective contents of the Al 2 O 3 component and the Ga 2 O 3 component is preferably 15.0%, more preferably 8.0%, and more preferably 3.0%. The Al 2 O 3 component and the Ga 2 O 3 component can use Al 2 O 3 , Al(OH) 3 , AlF 3 , Ga 2 O 3 , Ga(OH) 3, etc. as raw materials.
Bi 2O 3成分為其含量大於0%時,可提高折射率,並能夠降低玻璃轉移點的任意成分。 另一方面,藉由將Bi 2O 3成分的含量設為10.0%以下,可提高玻璃的耐失透性,且可減少玻璃的著色而提高可見光穿透率。因此,Bi 2O 3成分的含量,其上限以10.0%為佳,較佳是5.0%,更佳是3.0%。 Bi 2O 3成分,可使用Bi 2O 3等作為原料。 The Bi 2 O 3 component is any component that can increase the refractive index and lower the glass transition point when the content exceeds 0%. On the other hand, by setting the content of the Bi 2 O 3 component to 10.0% or less, the devitrification resistance of the glass can be improved, the coloring of the glass can be reduced, and the visible light transmittance can be improved. Therefore, the upper limit of the content of the Bi 2 O 3 component is preferably 10.0%, more preferably 5.0%, and more preferably 3.0%. As the Bi 2 O 3 component, Bi 2 O 3 or the like can be used as a raw material.
TeO 2成分為其含量大於0%時,可提高折射率,且能夠降低玻璃轉移點的任意成分。 然而,將玻璃原料置於鉑製的坩堝、或是置於與熔融玻璃接觸的部分是在鉑所形成的熔融槽中進行熔融時,存在著TeO 2成分有可能會與鉑合金化的問題。因此,TeO 2成分的含量,其上限以10.0%為佳,較佳是5.0%,更佳是3.0%,進而更佳是不含有。 TeO 2成分,可使用TeO 2等作為原料。 The TeO 2 component is any component that can increase the refractive index and lower the glass transition point when the content is greater than 0%. However, there is a problem that the TeO 2 component may be alloyed with platinum when the glass raw material is placed in a crucible made of platinum or when the part in contact with the molten glass is placed in a melting tank made of platinum. Therefore, the upper limit of the content of the TeO 2 component is preferably 10.0%, more preferably 5.0%, more preferably 3.0%, and more preferably none. TeO 2 component, TeO 2 etc. can be used as raw materials.
SnO 2成分為其含量大於0%時,可降低熔融玻璃的氧化而使熔融玻璃清澈,且不易使玻璃的光線穿透率惡化的任意成分。 另一方面,藉由將SnO 2成分的含量設為3.0%以下,不易發生因熔融玻璃的還原而引起的玻璃著色、或是玻璃失透。此外,由於SnO 2成分與熔解設備(特別是Pt等貴金屬)的合金化減少,而可期望熔融設備的使用年限延長。因此,SnO 2成分的含量設為3.0%以下為佳,較佳是低於2.0%,更佳是低於1.0%,進而更佳是不含有。 SnO 2成分,可使用SnO、SnO 2、SnF 2、SnF 4等作為原料。 The SnO 2 component is any component that, when the content is greater than 0%, can reduce the oxidation of the molten glass to make the molten glass clear, and is less likely to deteriorate the light transmittance of the glass. On the other hand, by setting the content of the SnO 2 component to 3.0% or less, glass coloring or glass devitrification due to reduction of molten glass is less likely to occur. In addition, since the SnO 2 component is less alloyed with the melting equipment (especially noble metals such as Pt), the service life of the melting equipment can be expected to be extended. Therefore, the content of the SnO 2 component is preferably 3.0% or less, more preferably less than 2.0%, more preferably less than 1.0%, and even more preferably not included. As the SnO 2 component, SnO, SnO 2 , SnF 2 , SnF 4 , etc. can be used as raw materials.
Sb 2O 3成分為其含量大於0%時,能夠使熔融玻璃消泡的任意成分。 另一方面,藉由將Sb 2O 3成分的含量設為1.0%以下,可使得過度的發泡難以發生,且與熔解設備(特別是Pt等貴金屬)的合金化減少。因此,Sb 2O 3成分的含量設為1.0%以下為佳,較佳是低於0.5%,更佳是低於0.3%,進而更佳是低於0.1%。 Sb 2O 3成分,可使用Sb 2O 3、Sb 2O 5、Na 2H 2Sb 2O 7・5H 2O等作為原料。 The Sb 2 O 3 component is any component capable of defoaming molten glass when its content is greater than 0%. On the other hand, by setting the content of the Sb 2 O 3 component to 1.0% or less, excessive foaming is less likely to occur, and alloying with melting equipment (especially noble metals such as Pt) can be reduced. Therefore, the content of the Sb 2 O 3 component is preferably 1.0% or less, more preferably less than 0.5%, more preferably less than 0.3%, still more preferably less than 0.1%. As the Sb 2 O 3 component, Sb 2 O 3 , Sb 2 O 5 , Na 2 H 2 Sb 2 O 7 ·5H 2 O, etc. can be used as raw materials.
此外,使玻璃澄清並消泡的成分,並不限於上述的Sb 2O 3成分,可使用玻璃製造的領域中周知的澄清劑、消泡劑或該等的組合。 In addition, the component that clarifies and defoams the glass is not limited to the above-mentioned Sb 2 O 3 component, and clarifiers, defoaming agents, or combinations thereof that are well-known in the field of glass manufacturing can be used.
F成分為其含量大於0%時,可提高玻璃的阿貝數,降低玻璃轉移點,且能夠提高耐失透性的任意成分。 然而,F成分的含量,亦即作為將上述各金屬元素的1種或2種以上的氧化物的一部分或全部置換的氟化物的F之合計量若大於10.0%,會使得F成分的揮發量變多,因此變得難以獲得安定的光學常數,而難以獲得均質的玻璃。此外,阿貝數會上升至大於所需的程度。 因此,F成分的含量設為10.0%以下為佳,較佳是低於5.0%,更佳是低於3.0%,進而更佳是低於1.0%,再進而更佳是不含有。 <關於不應該含有的成分> 接下來,對於本發明的光學玻璃中不應該含有的成分,以及不適合含有的成分進行說明。 The F component is any component that, when the content is greater than 0%, can increase the Abbe number of the glass, lower the glass transition point, and improve the devitrification resistance. However, if the content of the F component, that is, the total amount of fluoride that replaces part or all of one or more oxides of each metal element, is greater than 10.0%, the volatilization amount of the F component will change. Therefore, it becomes difficult to obtain stable optical constants and homogeneous glass. Furthermore, the Abbe number will rise to a level greater than required. Therefore, the content of the F component is preferably 10.0% or less, preferably less than 5.0%, more preferably less than 3.0%, still more preferably less than 1.0%, still more preferably not included. <About ingredients that should not be included> Next, components that should not be contained in the optical glass of the present invention and components that are not suitable to be contained will be described.
本發明的光學玻璃中,在不影響本發明的玻璃特性之範圍內,依所需可添加其他成分。但GeO 2成分會使得玻璃的色散性提高,實質上不含有為佳。 In the optical glass of the present invention, other components may be added as necessary within the scope that does not affect the properties of the glass of the present invention. However, the GeO 2 component will increase the dispersion of the glass, so it is better not to contain it substantially.
此外,除了Ti、Zr、Nb、W、La、Gd、Y、Yb、Lu的各種過渡金屬成分,例如Hf、V、Cr、Mn、Fe、Co、Ni、Cu、Ag、Mo、Ce、Nd等,具有分別以單獨或是複合型態含有時,即便是少量含有仍會使玻璃著色,吸收可見光區域的特定波長的光這樣的性質,因此,特別是在使用可見光區域的波長的光學玻璃中,實質上不含有為佳。In addition, various transition metal components other than Ti, Zr, Nb, W, La, Gd, Y, Yb, Lu, such as Hf, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Mo, Ce, Nd When contained individually or in a composite form, even a small amount will color the glass and absorb light of a specific wavelength in the visible light range. Therefore, it is particularly useful in optical glass using wavelengths in the visible light range. , it is better not to contain it in essence.
此外,PbO等鉛化合物及As 2O 3等砷化合物,以及Th、Cd、Tl、Os、Be、Se各成分,近年來,被視為有害的化學物質,而有避免使用的傾向,不僅是在玻璃的製造步驟,甚至於加工步驟及製品化後的處理,必須有因應環境對策上的處置。因此,在重視環境上的影響的情況下,除了無法避免的混入,實質上不含有該等成分為佳。藉此,使得光學玻璃能夠實質地不含有污染環境的物質。因此,即使不採取特別的環境對策措施,仍能夠製造、加工及廢棄該光學玻璃。 In addition, lead compounds such as PbO and arsenic compounds such as As 2 O 3 , as well as components such as Th, Cd, Tl, Os, Be, and Se, have been regarded as harmful chemical substances in recent years, and their use has tended to be avoided. Not only In the manufacturing steps of glass, even the processing steps and post-product treatment, environmental countermeasures must be taken. Therefore, when taking the environmental impact into consideration, it is better to substantially not contain these components except for unavoidable mixing. In this way, the optical glass can be substantially free of substances that pollute the environment. Therefore, the optical glass can be manufactured, processed and discarded without taking special environmental countermeasures.
[製造方法] 本發明的光學玻璃,例如能夠以下述方式加以製作。亦即,使各成分在規定的含量範圍內,將上述原料均勻地混合,再將製作出的混合物放入鉑坩堝、石英坩堝或鋁氧坩堝中進行初步熔融之後,再放入金坩堝、鉑坩堝、鉑合金坩堝、或銥坩堝中,於900℃至1400℃的溫度範圍下花費1小時至5小時進行熔融,攪拌使其均質化並進行消泡等步驟後,降溫至1300℃以下,接著進行最終階段的攪拌以去除條紋,再使用成形模具加以成形,藉此製作而成。在此,作為獲得使用成形模具成形的玻璃之方法,可舉出如將熔融玻璃流入成形模具一端的同時,由成形模具的另一端拉引出已成形的玻璃之方法、或是將熔融玻璃澆鑄於鑄模中,再使其緩冷卻之方法。 [Manufacturing method] The optical glass of the present invention can be produced in the following manner, for example. That is, the above-mentioned raw materials are uniformly mixed so that each component is within the prescribed content range, and then the prepared mixture is put into a platinum crucible, quartz crucible, or alumina-oxygen crucible for preliminary melting, and then a gold crucible, platinum crucible, and platinum crucible are added. In a crucible, platinum alloy crucible, or iridium crucible, it takes 1 hour to 5 hours to melt in the temperature range of 900°C to 1400°C, stir to homogenize, defoaming, etc., then cool down to below 1300°C, and then It is produced by performing final stirring to remove streaks and then shaping it using a mold. Here, as a method of obtaining glass formed using a forming mold, a method in which molten glass is poured into one end of the forming mold and the formed glass is pulled out from the other end of the forming mold, or a method in which the molten glass is cast in A method of slowly cooling the mold in the mold.
[物性] 本發明的光學玻璃,以具有高折射率及高色散為佳。 特別是,本發明的光學玻璃的折射率(n d),其下限以1.90為佳,較佳是1.95,更佳是1.98。該折射率的上限,以2.20為佳,較佳是2.15以下,更佳亦可為低於2.10。 此外,本發明的光學玻璃的阿貝數(ν d),其下限以15.0為佳,較佳是18.0以上,更佳是20.0以上,而其上限以30.0以下為佳,較佳是28.0以下,更佳是27.0。 通過具有如此高的折射率,即使期望光學元件的薄型化,亦能夠獲得大的折射量。此外,通過具有如此高的色散,當例如與具有低色散(高阿貝數)的光學元件組合時,能夠實現高成像特性。 因此,本發明的光學玻璃,可於光學設計上發揮功效,特別是,除了能夠期望高成像特性等之外,亦能夠實現光學系統的小型化,而使得光學設計上的自由度增加。 [Physical Properties] The optical glass of the present invention preferably has a high refractive index and high dispersion. In particular, the lower limit of the refractive index (n d ) of the optical glass of the present invention is preferably 1.90, more preferably 1.95, and more preferably 1.98. The upper limit of the refractive index is preferably 2.20, more preferably less than 2.15, more preferably less than 2.10. In addition, the lower limit of the Abbe number (ν d ) of the optical glass of the present invention is preferably 15.0, preferably 18.0 or more, and more preferably 20.0 or more, and the upper limit is preferably 30.0 or less, preferably 28.0 or less. Even better is 27.0. By having such a high refractive index, even if it is desired to reduce the thickness of the optical element, a large refractive amount can be obtained. Furthermore, by having such high dispersion, high imaging characteristics can be achieved when, for example, combined with an optical element having low dispersion (high Abbe number). Therefore, the optical glass of the present invention can play an important role in optical design. In particular, in addition to expecting high imaging properties, it can also achieve miniaturization of the optical system, thereby increasing the degree of freedom in optical design.
本發明的光學玻璃,較佳是可見光穿透率為高,尤其是可見光中短波長方面的光之穿透率為高,藉此,使得著色情況較少。 特別是,本發明的光學玻璃,若以玻璃的穿透率來表示,於厚度為10mm的樣品中表示分光穿透率70%的波長(λ 70),其上限以500nm為佳,較佳是490nm,更佳是480nm。 此外,本發明的光學玻璃中,於厚度為10mm的樣品中表示分光透過率5%之最短波長(λ 5),其上限以400nm為佳,較佳是390nm。 由此,玻璃的吸收邊緣變成在紫外光區附近,可提高玻璃對於可見光的透明性,因此,該光學玻璃可適用於如透鏡這種使光穿透的光學元件。 The optical glass of the present invention preferably has a high transmittance of visible light, especially a high transmittance of light with short wavelengths in visible light, thereby reducing coloring. In particular, if the optical glass of the present invention is expressed in terms of glass transmittance, in a sample with a thickness of 10 mm, the wavelength (λ 70 ) at which the spectral transmittance is 70% is expressed, and the upper limit is preferably 500 nm, preferably 500 nm. 490nm, preferably 480nm. In addition, in the optical glass of the present invention, the shortest wavelength (λ 5 ) showing a spectral transmittance of 5% in a sample with a thickness of 10 mm has an upper limit of 400 nm, preferably 390 nm. As a result, the absorption edge of the glass becomes near the ultraviolet light region, which can improve the transparency of the glass to visible light. Therefore, the optical glass can be suitable for optical elements that transmit light, such as lenses.
本發明的光學玻璃,較佳是具有高部分色散比(θg,F)。更具體而言,本發明的光學玻璃的部分色散比(θg,F),其下限以0.570為佳,較佳是0.580,更佳是0.595,進而更佳是0.605,再進而更佳是0.612。 此外,本發明的光學玻璃的部分色散比(θg,F),其與阿貝數(ν d)的關係,較佳是符合(−0.00162ν d+0.645)≦(θg,F)≦(−0.00162ν d+0.680)的關係。 藉此,因可獲得部分色散比(θg,F)為小的光學玻璃,光學玻璃可於降低光學元件的色像差等上發揮作用。 因此,本發明的光學玻璃的部分色散比(θg,F),其下限以(−0.00162ν d+0.645)為佳,較佳是(−0.00162ν d+0.650)。另一方面,本發明的光學玻璃的部分色散比(θg,F),其上限以(−0.00162ν d+0.675)為佳,較佳是(−0.00162ν d+0.670)。 The optical glass of the present invention preferably has a high partial dispersion ratio (θg, F). More specifically, the lower limit of the partial dispersion ratio (θg, F) of the optical glass of the present invention is preferably 0.570, more preferably 0.580, more preferably 0.595, still more preferably 0.605, still more preferably 0.612. In addition, the relationship between the partial dispersion ratio (θg,F) of the optical glass of the present invention and the Abbe number (ν d ) is preferably in line with (−0.00162ν d +0.645)≦(θg,F)≦(− 0.00162ν d +0.680) relationship. Thereby, optical glass with a small partial dispersion ratio (θg, F) can be obtained, and the optical glass can play a role in reducing chromatic aberration of optical elements. Therefore, the lower limit of the partial dispersion ratio (θg, F) of the optical glass of the present invention is preferably (−0.00162ν d +0.645), and more preferably (−0.00162ν d +0.650). On the other hand, the upper limit of the partial dispersion ratio (θg, F) of the optical glass of the present invention is preferably (−0.00162ν d +0.675), and more preferably (−0.00162ν d +0.670).
上述部分色散比(θg,F)與阿貝數(ν d)的關係式,於以部分色散比為縱軸,阿貝數為橫軸的直角座標中,是使用與法線為平行的直線來表示。法線,是表示在以往周知的玻璃的部分色散比(θg,F)與阿貝數(ν d)之間所觀察到的線性關係,於採用以部分色散比(θg,F)為縱軸,阿貝數(ν d)為橫軸的直角座標上,是藉由將標記NSL7與PBM2的部分色散比以及阿貝數之2點加以連接的直線來表示(請參考第1圖)。再者,以往周知的玻璃的部分色散比與阿貝數的關係,大致上是與法線重複。 在此,NSL7與PBM2是小原公司製的光學玻璃,PBM2的阿貝數(ν d)是36.3,部分色散比(θg,F)是0.5828,NSL7的阿貝數(ν d)是60.5,部分色散比(θg,F)是0.5436。 The above relationship between the partial dispersion ratio (θg,F) and the Abbe number (ν d ) is based on a straight line parallel to the normal in a rectangular coordinate system with the partial dispersion ratio as the vertical axis and the Abbe number as the horizontal axis. to express. The normal line represents the linear relationship observed between the partial dispersion ratio (θg, F) and the Abbe number (ν d ) of conventionally known glasses. Here, the partial dispersion ratio (θg, F) is used as the vertical axis. , the Abbe number (ν d ) is a rectangular coordinate on the horizontal axis, and is represented by a straight line connecting the two points labeled NSL7 and PBM2, the partial dispersion ratio and the Abbe number (please refer to Figure 1). Furthermore, the relationship between the partial dispersion ratio and the Abbe number of glass that has been known in the past is roughly the same as that of the normal line. Here, NSL7 and PBM2 are optical glasses manufactured by Ohara Corporation. The Abbe number (ν d ) of PBM2 is 36.3 and the partial dispersion ratio (θg, F) is 0.5828. The Abbe number (ν d ) of NSL7 is 60.5. The dispersion ratio (θg,F) is 0.5436.
[預成形體及光學元件] 可使用例如研磨加工的方法,或是再熱壓製成形、精密壓製成形等模壓成形的方法,由製成的光學玻璃來製作出玻璃成形體。亦即,能夠以下述列舉之方式製作玻璃成形體:對光學玻璃進行研削及研磨等機械加工來製作玻璃成形體;對由光學玻璃製作的預成形體,進行再熱壓製成形後,再進行研磨加工來製作玻璃成形體;對進行研磨加工來製作的預成形體,或是藉由周知的漂浮成形等所成形的預成形體,進行精密壓製成形,來製作玻璃成形體等。但製作玻璃成形體的方法,並不限於上述。 [Preforms and optical components] A glass molded body can be produced from the optical glass produced by, for example, grinding processing, or press molding methods such as reheat press molding and precision press molding. That is, a glass molded body can be produced in the following manner: the optical glass is subjected to mechanical processing such as grinding and grinding to produce a glass molded body; a preform made of optical glass is reheated and pressed into shape, and then polished. Processing to produce a glass molded body; Preformed bodies produced by grinding or preforms molded by well-known float molding, etc., are precision press-molded to produce glass molded bodies, etc. However, the method of producing a glass formed body is not limited to the above.
像這樣,由本發明的光學玻璃所形成的玻璃成形體,能夠在各式各樣的光學元件及光學設計上發揮功效,其中特別適合用於透鏡或稜鏡等光學元件。藉由提高玻璃的安定性,可形成口徑大的玻璃成形體,因此,除了能夠期望光學元件的大型化之外,使用於相機或投影機等光學機器時,亦能夠實現高清晰且高精密度的成像特性及投影特性。 [實施例] In this way, the glass molded body formed of the optical glass of the present invention can be used in various optical elements and optical designs, and is particularly suitable for use in optical elements such as lenses and lenses. By improving the stability of the glass, a glass molded body with a large diameter can be formed. Therefore, in addition to the enlargement of optical elements, it is also possible to achieve high definition and high precision when used in optical equipment such as cameras and projectors. imaging characteristics and projection characteristics. [Example]
本發明實施例(No.1至No.52)的玻璃組成,與該等玻璃的折射率(n d)、阿貝數(ν d)、穿透率(λ 5、λ 70)、以及部分色散比(θg,F)的數值皆示於表1至表10。此外,以下的實施例僅作為例示之目的,本發明並不限於該等實施例。 The glass compositions of the embodiments of the present invention (No. 1 to No. 52), and the refractive index (n d ), Abbe number (ν d ), transmittance (λ 5 , λ 70 ), and partial The values of the dispersion ratio (θg, F) are shown in Table 1 to Table 10. In addition, the following examples are only for illustrative purposes, and the present invention is not limited to these examples.
實施例的玻璃,各成分的原料,皆是選擇與其相符合的氧化物、氫氧化物、碳酸鹽、硝酸鹽、氟化物、氫氧化物、偏磷酸化合物等一般光學玻璃所使用的高純度原料,之後再將該等原料進行秤重並均勻地混合後,放入鉑坩堝,並以溫度設定為1280℃至1340℃範圍的電爐,花費2.5小時來進行玻璃原料的熔解,以及攪拌熔解的玻璃原料使其消泡後,降溫至1180℃至1250℃,再次進行攪拌使其均質化,接著澆鑄於鑄模中,再加以緩冷卻而製作出玻璃。The raw materials of each component of the glass in the examples are selected from high-purity raw materials used in general optical glass such as oxides, hydroxides, carbonates, nitrates, fluorides, hydroxides, and metaphosphate compounds. , then weigh the raw materials and mix them evenly, put them into a platinum crucible, and use an electric furnace with a temperature set in the range of 1280°C to 1340°C. It takes 2.5 hours to melt the glass raw materials and stir the melted glass. After the raw materials are defoamed, the temperature is lowered to 1180°C to 1250°C, stirred again to homogenize, cast into a mold, and slowly cooled to produce glass.
實施例的玻璃折射率(n d)及阿貝數(ν d),是以相對於氦燈的d線(587.56nm)之測定值來表示。此外,阿貝數(ν d),是使用上述d線的折射率、相對於氫燈的F線(486.13nm)之折射率(n F)、相對於C線(656.27nm)之折射率(n C)的數值,由阿貝數(ν d)=[(n d−1)/(n F−n C)]之數式所計算出。 部分色散比,是測定C線(波長656.27nm)中的折射率n C、F線(波長486.13nm)中的折射率n F、g線(波長435.835nm)中的折射率n g,再藉由(θg,F)=(n g−n F)/(n F−n C)之數式,計算出該部分色散比。 The refractive index (n d ) and Abbe's number (ν d ) of the glass in Examples are expressed as measured values relative to the d line (587.56 nm) of a helium lamp. In addition, the Abbe number (ν d ) is calculated using the refractive index of the d line mentioned above, the refractive index (n F ) with respect to the F line (486.13 nm) of the hydrogen lamp, and the refractive index (n F ) with respect to the C line (656.27 nm). The value of n C ) is calculated from the expression Abbe number (ν d )=[(n d −1)/(n F −n C )]. The partial dispersion ratio is to measure the refractive index n C in the C line (wavelength 656.27nm), the refractive index n F in the F line (wavelength 486.13nm), and the refractive index n g in the g line (wavelength 435.835nm), and then borrow This part of the dispersion ratio is calculated from the formula (θg,F)=(n g −n F )/(n F −n C ).
實施例的玻璃的穿透率,是根據日本光學玻璃工業會規格JOGIS02-2003來加以測定。此外,本發明中,藉由測定玻璃的穿透率來求得玻璃有無著色及其著色程度。具體而言,是將厚度為10±0.1mm相對平行的研磨品,根據JISZ8722,測定200nm至800nm的分光穿透率,而求得λ 5(穿透率為5%時的波長)及λ 70(穿透率為70%時的波長)。 此外,本測定所使用的玻璃,是使用緩冷卻降溫速度設為−25℃/hr,以緩冷卻爐進行處理之物。 The transmittance of the glass of the Example was measured based on the Japan Optical Glass Industry Association standard JOGIS02-2003. In addition, in the present invention, the presence or absence of coloring of the glass and the degree of coloring are determined by measuring the transmittance of the glass. Specifically, the spectral transmittance from 200 nm to 800 nm is measured according to JISZ8722 on relatively parallel abrasive articles with a thickness of 10±0.1 mm, and λ 5 (wavelength at which the transmittance is 5%) and λ 70 are obtained. (Wavelength when transmittance is 70%). In addition, the glass used in this measurement was processed in a slow cooling furnace with a slow cooling rate of −25°C/hr.
[表1]
[表2]
[表3]
[表4]
[表5]
[表6]
[表7]
[表8]
[表9]
[表10]
如表所示,本發明實施例的光學玻璃,不論何者,其折射率(n d)皆為1.90以上,並且,該折射率(n d)亦為2.20以下,更詳細而言是2.10以下,皆在所期望的範圍內。 此外,本發明實施例的光學玻璃,不論何者,其阿貝數(ν d)皆為30.0以下,更具體而言是28.0以下,並且,該阿貝數(ν d)亦為15.0以上,更詳細而言是20.0以上,皆在所期望的範圍內。 As shown in the table, the refractive index (n d ) of the optical glass according to the embodiment of the present invention is 1.90 or more, and the refractive index (n d ) is also 2.20 or less, and more specifically, it is 2.10 or less. All within the expected range. In addition, the Abbe number (ν d ) of the optical glass according to the embodiment of the present invention is 30.0 or less, more specifically, 28.0 or less, and the Abbe number (ν d ) is also 15.0 or more, and more specifically, the Abbe number (ν d ) is 15.0 or more. Specifically, it is above 20.0, which is within the expected range.
此外,本發明實施例的光學玻璃,λ 70(穿透率為70%時的波長)皆為500nm以下,更詳細而言是490nm以下。此外,本發明實施例的光學玻璃,λ 5(穿透率為5%時的波長)皆為400nm以下,更詳細而言是390nm以下。 In addition, in the optical glass according to the embodiments of the present invention, λ 70 (the wavelength when the transmittance is 70%) is all 500 nm or less, and more specifically, 490 nm or less. In addition, in the optical glass according to the embodiments of the present invention, λ 5 (wavelength when the transmittance is 5%) is all 400 nm or less, and more specifically, 390 nm or less.
此外,本發明實施例的光學玻璃,不論何者,其部分色散比(θg,F)皆為(−0.00162ν d+0.645)以上,更詳細而言是(−0.00162ν d+0.650)以上。 與之相反,本發明實施例的光學玻璃的部分色散比為(−0.00162ν d+0.680)以下,更詳細而言是(−0.00162ν d+0.670)以下。因此可知,該等部分色散比(θg,F)在所期望的範圍內。 In addition, regardless of the optical glass according to the embodiment of the present invention, the partial dispersion ratio (θg, F) is (−0.00162ν d +0.645) or more, and more specifically, it is (−0.00162ν d +0.650) or more. On the contrary, the partial dispersion ratio of the optical glass according to the embodiment of the present invention is (−0.00162ν d +0.680) or less, and more specifically, it is (−0.00162ν d +0.670) or less. Therefore, it can be seen that the partial dispersion ratios (θg, F) are within the desired range.
因此,可清楚得知,本發明實施例的光學玻璃,除了可使折射率及阿貝數在所期望的範圍內之外,亦能夠價格低廉地製作,且可使著色減少。Therefore, it is clear that the optical glass according to the embodiment of the present invention can not only have the refractive index and Abbe number within the desired range, but can also be produced at low cost and can reduce coloration.
再者,使用以本發明實施例所獲得的光學玻璃,於進行了再熱壓製成形之後,進行了研削及研磨,加工成透鏡及稜鏡的形狀。此外,使用本發明實施例的光學玻璃,形成精密壓製成形用預成形體,再將該精密壓製成形用預成形體進行了精密壓製成形。不管是何種情況,加熱軟化後的玻璃不會發生乳白化及失透等問題而能夠安定地加工成各式各樣的透鏡與稜鏡的形狀。Furthermore, the optical glass obtained according to the embodiment of the present invention was reheated and pressed into shape, and then grinded and polished to be processed into the shapes of lenses and lenses. Furthermore, the optical glass according to the embodiment of the present invention was used to form a preform for precision press molding, and then the preform for precision press molding was precision press-formed. Regardless of the situation, glass softened by heating will not cause problems such as opalescence and devitrification, and can be stably processed into a variety of lens and lens shapes.
以上,雖然以例示之目的詳細地說明了本發明,但本實施例的目的僅止於例示,所屬技術領域中具有通常知識者應可理解,在不偏離本發明的思想及範圍的情況下,本發明仍可進行許多變更。Although the present invention has been described in detail for the purpose of illustration, the purpose of this embodiment is only illustrative. It should be understood by those with ordinary skill in the technical field that without departing from the spirit and scope of the present invention, The invention is still susceptible to many variations.
[圖1]係以部分色散比(θg,F)為縱軸,阿貝數(ν d)為橫軸的直角座標所表示的法線之示意圖。 [圖2]係本發明實施例玻璃的部分色散比(θg,F)與阿貝數(ν d)關係之示意圖。 [Fig. 1] is a schematic diagram showing the normal line represented by rectangular coordinates with the partial dispersion ratio (θg, F) as the vertical axis and the Abbe number (ν d ) as the horizontal axis. [Fig. 2] is a schematic diagram showing the relationship between the partial dispersion ratio (θg, F) and the Abbe number (ν d ) of the glass according to the embodiment of the present invention.
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JP4446982B2 (en) | 2005-09-21 | 2010-04-07 | Hoya株式会社 | Optical glass, glass gob for press molding, glass molded body, optical element and production method thereof |
CN101289276B (en) | 2008-06-19 | 2011-08-31 | 成都光明光电股份有限公司 | High-refraction and high- dispersion optical glass and method of manufacture |
JP5461420B2 (en) | 2008-11-10 | 2014-04-02 | Hoya株式会社 | Manufacturing method of glass, optical glass, glass material for press molding, optical element and manufacturing method thereof |
JP2011153048A (en) | 2010-01-28 | 2011-08-11 | Konica Minolta Opto Inc | Optical glass |
JP5766002B2 (en) | 2011-04-25 | 2015-08-19 | Hoya株式会社 | Optical glass, glass material for press molding, optical element and manufacturing method thereof, and bonded optical element |
CN102503121B (en) | 2011-10-08 | 2013-09-18 | 成都光明光电股份有限公司 | Optical glass and optical element |
JP5979371B2 (en) | 2012-10-19 | 2016-08-24 | Hoya株式会社 | Caret, optical glass and method for producing them |
JP2015127281A (en) | 2013-12-27 | 2015-07-09 | 株式会社オハラ | Glass |
CN104788018B (en) | 2014-01-22 | 2019-03-05 | 成都光明光电股份有限公司 | High-refractive and high-dispersive optical glass, optical element and optical instrument |
JP6509525B2 (en) | 2014-10-30 | 2019-05-08 | 株式会社オハラ | Optical glass, preform and optical element |
-
2017
- 2017-11-13 JP JP2017218657A patent/JP7410634B2/en active Active
- 2017-11-29 TW TW106141614A patent/TWI821167B/en active
- 2017-11-29 TW TW112137993A patent/TW202402695A/en unknown
- 2017-12-01 CN CN202310219632.6A patent/CN116332506A/en active Pending
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2023
- 2023-11-02 JP JP2023188630A patent/JP2024003105A/en active Pending
Also Published As
Publication number | Publication date |
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JP2018090473A (en) | 2018-06-14 |
TW201827372A (en) | 2018-08-01 |
JP2024003105A (en) | 2024-01-11 |
TWI821167B (en) | 2023-11-11 |
JP7410634B2 (en) | 2024-01-10 |
CN116332506A (en) | 2023-06-27 |
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