CN117510064A - Optical glass, optical element, and optical device - Google Patents
Optical glass, optical element, and optical device Download PDFInfo
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- CN117510064A CN117510064A CN202310962260.6A CN202310962260A CN117510064A CN 117510064 A CN117510064 A CN 117510064A CN 202310962260 A CN202310962260 A CN 202310962260A CN 117510064 A CN117510064 A CN 117510064A
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- 239000005304 optical glass Substances 0.000 title claims abstract description 46
- 230000003287 optical effect Effects 0.000 title claims abstract description 32
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 20
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 12
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 abstract description 13
- 239000011521 glass Substances 0.000 description 98
- 238000002834 transmittance Methods 0.000 description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 21
- 230000005484 gravity Effects 0.000 description 15
- 238000004031 devitrification Methods 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 229910052697 platinum Inorganic materials 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 4
- 229930006000 Sucrose Natural products 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 239000005720 sucrose Substances 0.000 description 4
- 230000003190 augmentative effect Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical class OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 239000000156 glass melt Substances 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium 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
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- 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)
- Glass Compositions (AREA)
Abstract
The invention relates to an optical glass, an optical element and an optical device. The invention provides an optical glass and an optical element which have high refractive index, high transmissivity, excellent universality and high productivity. La in mole% based on oxide of the optical glass 2 O 3 The components are 15.0 to 30.0 percent, the ZnO component is0 to 8.0 percent, the BaO component is0 to 10.0 percent, and the Rn is the same as the BaO component 2 The sum of the contents of the O components is more than 0% and 10.0% or less, the molar ratio (SiO 2 +B 2 O 3 )/(TiO 2 +ZrO 2 +Nb 2 O 5 ) At most 0.80, molar ratio (SiO 2 +B 2 O 3 )/Ln 2 O 3 A molar ratio Nb of 1.01 to 2.00 2 O 5 /(TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 ) Is 0.10 or more.
Description
Technical Field
The invention relates to an optical glass, an optical element and an optical device.
Background
The optical glass and the optical element can be used for applications in which optical characteristics of cameras, imaging devices, and the like are improved by combining lenses of different optical regions, applications in which they are installed in optical apparatuses to realize various optical designs, and the like. Recently, the market for optical devices equipped with augmented reality devices and virtual reality devices has also been expanding.
In particular, although optical glass having a high refractive index and a high transmittance has high versatility in use, it is necessary to increase TiO in order to increase the refractive index 2 Component, nb 2 O 5 Ingredients, WO 3 Component, bi 2 O 3 The content of the component and the like. However, these components are components that cause coloration of the glass from platinum during melting of the glass.
In addition, from the viewpoint of stably supplying an optical glass and improving productivity, it is important that the devitrification resistance in the production process and molding is high.
For example, japanese patent application laid-open No. 2015-040171A1 (patent document 1) proposes an oxide glass as an optical glass having a high refractive index, low dispersion and excellent glass stability, which contains Si in a total amount of 5 to 55% in terms of cation% 4+ And B 3+ 10 to 50 percent of La 3+ (La 3+ 、Gd 3+ 、Y 3+ And Yb 3+ 70% or less in total), 22 to 55% in total of Ti 4+ 、Nb 5+ 、Ta 5+ And W is 6+ ，Ti 4+ The content is 22% or less, [ Si ] 4 /(Si 4 +B 3+ )]Is less than 0.40 and La 3+ 、Gd 3+ 、Y 3+ 、Yb 3+ 、Zr 4+ 、Ti 4+ 、Nb 5+ 、Ta 5+ 、W 6+ And Bi (Bi) 3+ The total content of (2) is more than 65%, the Abbe number vd is in the range of 23-35, and the refractive index nd satisfies the formula nd is more than or equal to 2.205- (0.0062 Xvd). In addition, japanese patent application laid-open publication No. 2017-088482A1 (patent document 2), as an optical glass that can obtain a glass having high devitrification resistance at a lower price, an optical glass containing B in mol% has been proposed 2 O 3 ：5.0～50.0％、La 2 O 3 ：5.0～30.0％、SiO 2 ：0～25.0％、ZnO：0～45.0％、TiO 2 : more than 0 and less than 40.0 percent, zrO 2 :0 to 15.0% by mole of (Nb) 2 O 5 +WO 3 ) The optical glass has a refractive index (nd) of 1.75 or more, and an Abbe number (vd) of 25 or more and 48 or less, which is less than 10.0%.
Disclosure of Invention
Neither of the glasses disclosed in patent documents 1 and 2 can be said to have any one of a sufficient refractive index and transmittance, and cannot be said to be highly versatile glasses having a high refractive index and a high transmittance.
The present invention has been made in view of the above-described problems, and an object thereof is to obtain an optical glass and an optical element having a high refractive index, a high transmittance, excellent versatility, and high productivity.
As a result of intensive studies and intensive studies to solve the above-mentioned problems, the present inventors have found that La is contained 2 O 3 Composition and Rn 2 An O component, a ZnO component and a BaO component are suppressed, and the molar ratio (SiO 2 +B 2 O 3 )/(TiO 2 +ZrO 2 +Nb 2 O 5 ) Molar ratio (SiO) 2 +B 2 O 3 )/Ln 2 O 3 Molar ratio Nb 2 O 5 /(TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 ) Thus, an optical glass and an optical element having a high refractive index, high transmittance, excellent versatility, and high productivity can be obtained.
Specifically, the present invention provides the following optical glass, optical element, and optical device.
[1] An optical glass comprising, in mole% based on oxides:
La 2 O 3 the components are 15.0 to 30.0 percent,
ZnO is 0-8.0%,
the BaO component is0 to 10.0 percent,
Rn 2 the sum of the contents of O components (wherein Rn is 1 or more selected from the group consisting of Li, na, K) is more than 0% and 10.0% or less,
molar ratio (SiO) 2 +B 2 O 3 )/(TiO 2 +ZrO 2 +Nb 2 O 5 ) Is not more than 0.80 of the total weight of the composition,
molar ratio (SiO) 2 +B 2 O 3 )/Ln 2 O 3 (wherein Ln is 1 or more selected from the group consisting of La, Y, gd, yb) is 1.01 or more and 2.00 or less,
molar ratio Nb 2 O 5 /(TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 ) Is 0.10 or more.
[2]According to [1]]The optical glass has a refractive index (n d ) 1.98000.
[3] An optical element comprising the optical glass of [1] or [2 ].
[4] An optical device comprising the optical element according to [3 ].
According to the present invention, an optical glass and an optical element having a high refractive index, high transmittance, excellent versatility, and high productivity can be provided.
Detailed Description
Hereinafter, embodiments of the optical glass of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. Note that, although the description of the portions to be repeated is omitted appropriately, the gist of the present invention is not limited.
[ glass component ]
The composition ranges of the respective components constituting the optical glass of the present invention will be described below. In the present specification, unless otherwise specified, the content of each component is expressed as mole% relative to the total mole number of the glass converted into the oxide composition. The term "converted to an oxide composition" as used herein refers to a composition in which each component contained in the glass is expressed by taking the total mole number of the oxide to be formed as 100 mole% when all of the oxide, the complex salt, the metal fluoride, and the like used as the raw materials of the constituent components of the glass of the present invention are decomposed to become an oxide in melting.
La 2 O 3 The component is a component which is less likely to cause glass coloration than other high refractive index components and can improve the refractive index, but when the content is large, stability is impaired and specific gravity is increased. Therefore La 2 O 3 The lower limit of the content of the component is preferably 15.0% or more, more preferably 16.0% or more, and even more preferably 17.0% or more. La on the other hand 2 O 3 Upper limit of the content of the componentPreferably 30.0% or less, more preferably 29.0% or less, and even more preferably 28.0% or less.
Y 2 O 3 The component (b) is a component for increasing the refractive index of the glass, and is a component having a small specific gravity in the rare earth oxide, but if the content is large, stability is impaired. Thus Y 2 O 3 The lower limit of the content of the component is preferably more than 0%, more preferably 0.5% or more, and still more preferably 1.0% or more. On the other hand, Y 2 O 3 The upper limit of the content of the component is preferably 10.0% or less, more preferably 8.0% or less, and even more preferably 5.0% or less.
SiO 2 The component (A) promotes stable glass formation and improves the devitrification resistance of the glass. But the refractive index decreases with a larger content. Thus, siO 2 The upper limit of the content of the component is preferably 30.0% or less, more preferably 28.0% or less, further preferably 25.0% or less, further preferably 23.0% or less, further preferably 20.0% or less. On the other hand, siO 2 The lower limit of the content of the component may be 0%, but is preferably more than 0%, more preferably 1.0% or more, further preferably 2.0% or more, further preferably 3.0% or more, further preferably 4.0% or more, further preferably 5.0% or more.
B 2 O 3 The component (c) is a component that promotes stable glass formation and improves the devitrification resistance of the glass. By combining with La 2 O 3 The components are contained together to improve stability. Thus B 2 O 3 The upper limit of the content of the component is preferably 40.0% or less, more preferably 38.0% or less, further preferably 35.0% or less, further preferably 33.0% or less, further preferably 32.0% or less, further preferably 30.0% or less. On the other hand, B 2 O 3 The lower limit of the content of the component is preferably set to be more than 0%, more preferably 1.0% or more, further preferably 3.0% or more, further preferably 5.0% or more, further preferably 6.0% or more, further preferably 8.0% or more.
TiO 2 The component (a) is a component that increases the refractive index and Abbe number of the glass, but when it is contained in excess, the glass is colored. Thus, tiO 2 The upper limit of the content of the component is preferably 55.0% or less, more preferably 53.0% or less, further preferably 50.0% or less, further preferably 48.0% or less. On the other hand, tiO 2 The lower limit of the content of the component is preferably set to be more than 0%, more preferably 3.0% or more, further preferably 5.0% or more, further preferably 8.0% or more, further preferably 10.0% or more, further preferably 15.0% or more, further preferably 18.0% or more, further preferably 20.0% or more.
Nb 2 O 5 The components are capable of increasing the refractive index and Abbe number of the glass and are mixed with TiO 2 The components are contained together to improve stability. However, when the content is excessive, the specific gravity becomes large. Thus, nb 2 O 5 The upper limit of the content of the component is preferably 18.0% or less, more preferably 15.0% or less, still more preferably 12.0% or less, still more preferably 10.0% or less, and most preferably 9.0% or less. On the other hand, from the viewpoint of improving stability, nb 2 O 5 The lower limit of the content of the component is preferably 1.0% or more, more preferably 2.0% or more, still more preferably 3.0% or more, and may be 0% or more.
WO 3 Component, bi 2 O 3 The component (A) is a component which can increase the refractive index of the glass when the content is more than 0%, but when the content is more, the glass becomes colored, and the specific gravity becomes large. WO (WO) 3 Component, bi 2 O 3 The preferred ranges of the components are as follows.
WO 3 The upper limit of the content of the component is preferably 10.0% or less, more preferably 5.0% or less, still more preferably 3.0% or less, and most preferably 1.0% or less.
Bi 2 O 3 The upper limit of the content of the component is preferably 3.0% or less, more preferably 1.0% or less, further preferably 0.8% or less, further preferably 0.5% or less, further preferably 0.3% or less, and most preferably 1.0% or lessIs less than 0.1%.
ZrO 2 The component (c) is a component that can increase the refractive index and also can increase the transmittance. However, when the content is excessive, the workability of the glass by polishing, grinding, or the like is deteriorated. Thus, zrO 2 The upper limit of the content of the component is preferably 10.0% or less, more preferably 9.0% or less, and even more preferably 8.5% or less. On the other hand, zrO 2 The lower limit of the content of the component is preferably more than 0%, more preferably 1.0% or more, still more preferably 2.0% or more, still more preferably 3.0% or more, and may be 0%.
Li 2 O component, K 2 O component, na 2 The O component is a component that lowers the melting temperature of the glass, but when the content is large, the stability is impaired and devitrification is easy. Li (Li) 2 O component, K 2 O component, na 2 Li in O component 2 The component O is when combined with La 2 O 3 When the components are contained together, the components most capable of improving the stability of the glass are contained. Li (Li) 2 O component, K 2 O component, na 2 The preferable range of the O component is as follows.
K 2 The upper limit of the content of the O component is preferably 10.0% or less, more preferably 8.0% or less, further preferably 5.0% or less, further preferably 3.0% or less, further preferably 1.0% or less, further preferably 0.8% or less. On the other hand, K 2 The lower limit of the content of the O component is preferably set to be more than 0%, more preferably 0.1% or more, still more preferably 0.2% or more, still more preferably 0.3% or more, still more preferably 0.4% or more, and may be 0%.
Na 2 The upper limit of the content of the O component is preferably 10.0% or less, more preferably 8.0% or less, further preferably 5.0% or less, further preferably 3.0% or less, further preferably 1.0% or less, further preferably 0.8% or less. On the other hand, na 2 The lower limit of the content of the O component is preferably set to be more than 0%, more preferably 0.1% or more, still more preferably 0.2% or more, still more preferably 0.3% or more, still more preferably 0.1% or moreThe content is preferably 0.4% or more, but may be 0%.
The BaO component is a component for improving the stability of the glass, but in order to maintain the refractive index and abbe number, and because of its large specific gravity, it is preferable to reduce the content thereof in order to produce an optical glass having high versatility. In addition, from the viewpoint of maintaining acid resistance, the content is preferably reduced. Therefore, the upper limit of the content of the BaO component is preferably 10.0% or less, more preferably 8.0% or less, further preferably 7.0% or less, further preferably 6.0% or less, further preferably 5.0% or less, further preferably 4.0% or less, further preferably 3.0% or less, further preferably 2.0% or less, further preferably 1.0% or less.
The CaO component, mgO component, and SrO component are components that improve the devitrification resistance of the glass, but when the content is large, it is difficult to maintain the refractive index and abbe number. The preferable ranges of the CaO component, mgO component and SrO component are as follows.
The upper limit of the CaO component content is preferably 10.0% or less, more preferably 8.0% or less, further preferably 7.0% or less, further preferably 6.0% or less, further preferably 5.0% or less, further preferably 4.0% or less, further preferably 3.0% or less, further preferably 2.0% or less, further preferably 1.0% or less.
The upper limit of the content of the MgO component is preferably 10.0% or less, more preferably 8.0% or less, further preferably 7.0% or less, further preferably 6.0% or less, further preferably 5.0% or less, further preferably 4.0% or less, further preferably 3.0% or less, further preferably 2.0% or less, further preferably 1.0% or less.
The upper limit of the content of the SrO component is preferably 10.0% or less, more preferably 8.0% or less, further preferably 7.0% or less, further preferably 6.0% or less, further preferably 5.0% or less, further preferably 4.0% or less, further preferably 3.0% or less, further preferably 2.0% or less, further preferably 1.0% or less.
Gd 2 O 3 Component Yb 2 O 3 The component (a) is a component for increasing the refractive index of the glass, but if the content is large, the stability is impaired and the specific gravity becomes large. Gd (Gd) 2 O 3 Component Yb 2 O 3 The preferred ranges of the components are as follows.
Gd 2 O 3 The upper limit of the content of the component is preferably 5.0% or less, more preferably 3.0% or less, further preferably 2.0% or less, further preferably 1.0% or less, and most preferably 0.5% or less.
Yb 2 O 3 The upper limit of the content of the component is preferably 5.0% or less, more preferably 3.0% or less, further preferably 2.0% or less, further preferably 1.0% or less, and most preferably 0.5% or less.
Al 2 O 3 The component (a) is a component that improves the chemical durability of the glass and also improves the viscosity of the glass when molten. In particular, by combining Al 2 O 3 The content of the component is set to 5.0% or less, whereby the meltability of the glass can be improved and the devitrification tendency of the glass can be reduced. Thus, al 2 O 3 The upper limit of the content of the component is preferably 5.0% or less, more preferably 3.0% or less, most preferably 1.0% or less, and may be 0%.
The ZnO component is a component that lowers the liquidus temperature of the glass and improves the devitrification resistance of the glass, but when the content is large, it is difficult to maintain the refractive index and abbe number. In addition, from the viewpoint of maintaining acid resistance, the content is preferably reduced. Therefore, the upper limit of the content of the ZnO component is preferably 8.0% or less, more preferably 7.0% or less, further preferably 6.0% or less, further preferably 5.0% or less, further preferably 4.0% or less, further preferably 3.0% or less, further preferably 2.0% or less, further preferably 1.0% or less, and may be 0% or less.
Ta 2 O 5 The component (c) is a component that can improve the refractive index of the glass and improve the devitrification resistance of the glass. On the other hand, by combining Ta 2 O 5 The content of the components is set to 5.0%Ta as rare mineral resource 2 O 5 The amount of the components used is reduced, and the glass is easily melted at a lower temperature, so that the production cost of the glass can be reduced. In addition, ta may thereby be reduced 2 O 5 The excessive content of the components causes devitrification of the glass. Thus, ta 2 O 5 The upper limit of the content of the component is preferably 5.0% or less, more preferably 3.0% or less, still more preferably 1.0% or less, and may be 0%.
P 2 O 5 The upper limit of the content of the component is preferably 5.0% or less, more preferably 3.0% or less, further preferably 1.0% or less, further preferably 0.5% or less, and may be 0% or less.
The upper limit of the content of the F component is preferably 5.0% or less, more preferably 3.0% or less, still more preferably 1.0% or less, still more preferably 0.5% or less, still more preferably 0.3% or less, and may be 0% or less.
TeO 2 The upper limit of the content of the component is preferably 3.0% or less, more preferably 2.0% or less, still more preferably 1.0% or less, still more preferably 0.5% or less, and may be 0% or less.
Ga 2 O 3 The upper limit of the content of the component is preferably 3.0% or less, more preferably 2.0% or less, still more preferably 1.0% or less, still more preferably 0.5% or less, and may be 0% or less.
GeO 2 The upper limit of the content of the component is preferably 3.0% or less, more preferably 2.0% or less, still more preferably 1.0% or less, still more preferably 0.5% or less, and may be 0% or less.
CeO 2 The upper limit of the content of the component is preferably 3.0% or less, more preferably 2.0% or less, still more preferably 1.0% or less, still more preferably 0.5% or less, and may be 0% or less.
Er 2 O 3 Component, pr 2 O 3 The content of the component (a) is preferably 1.0% or less, more preferably 0.5% or less, still more preferably 0.1% or less, and most preferably substantially no component (a).
SnO 2 The upper limit of the content of the component is preferably 2.0% or less, more preferably 1.0% or less, still more preferably 0.5% or less, and may be 0%.
Sb 2 O 3 The component (A) is a component that promotes clarification and defoaming when melting glass, and is any component. Here, by bringing Sb into contact with 2 O 3 The content of the component is set to 0.1% or less, and particularly, coloring in the high refractive index glass can be suppressed. In addition, when the content is 0.1% or less, excessive foaming is less likely to occur during glass melting, and Sb can be caused 2 O 3 The components are not easily alloyed with melting equipment (particularly, noble metals such as Pt). Thus, sb 2 O 3 The upper limit of the content of the component is preferably 0.1% or less, more preferably 0.08% or less, still more preferably 0.05% or less, and may be 0%.
The components for refining and defoaming glass are not limited to the above Sb 2 O 3 As the component, a fining agent, a defoaming agent, or a combination thereof, which are known in the glass manufacturing field, may be used.
The component C is a component capable of maintaining a reducing atmosphere in the platinum crucible, suppressing the mixing of platinum into the glass due to oxidation, and improving the transmittance, but when the content is large, the cationic component in the glass is reduced, and the glass is colored. Therefore, the upper limit of the content of the component C is preferably 10.0% or less, more preferably 8.0% or less, still more preferably 6.0% or less, and most preferably 5.0% or less. On the other hand, the lower limit of the content of the component C is preferably more than 0%, more preferably 0.5% or more, still more preferably 1.0% or more, most preferably 2.0% or more, and may be 0%.
The S component is a component that can maintain a reducing atmosphere in the platinum crucible, inhibit platinum from being mixed into the glass by oxidation, and improve transmittance, but when the content is large, the cationic component in the glass is reduced, and the glass is colored. Therefore, the upper limit of the content of the S component is preferably 10.0% or less, more preferably 8.0% or less, still more preferably 6.0% or less, and most preferably 5.0% or less. On the other hand, the lower limit of the content of the S component is preferably set to be more than 0%, more preferably to be 0.5% or more, still more preferably to be 1.0% or more, most preferably to be 2.0% or more, and may be 0%.
The organic component such as sucrose is a component that can maintain a reducing atmosphere in the platinum crucible, inhibit platinum from being mixed into the glass by oxidation, and improve the transmittance, but when the content is large, the cationic component in the glass is reduced, and the glass is colored. Therefore, the upper limit of the content of the organic component such as sucrose is preferably 10.0% or less, more preferably 8.0% or less, still more preferably 6.0% or less, and most preferably 5.0% or less. On the other hand, the lower limit of the content of the organic component such as sucrose is preferably set to be more than 0%, more preferably to be 0.5% or more, still more preferably to be 1.0% or more, most preferably to be 2.0% or more, and may be 0%.
The component for reducing the glass is not limited to the above-mentioned organic component such as the C component, S component, sucrose, and the like, and a reducing agent or a combination thereof known in the glass manufacturing field may be used.
Ln 2 O 3 The sum (molar sum) of the contents of the components (in the formula, ln is one or more selected from the group consisting of La, Y, gd, yb) can increase the refractive index of the glass, but when the content is excessive, the devitrification of the glass can be increased. Thus Ln 2 O 3 The lower limit of the sum of the contents of the components is preferably 15.0% or more, more preferably 18.0% or more, and still more preferably 19.0% or more. On the other hand, ln 2 O 3 The upper limit of the sum of the contents of the components is preferably 40.0% or less, more preferably 35.0% or less, further preferably 33.0% or less, further preferably 30.0% or less.
Rn 2 The sum (molar sum) of the contents of the O component (in the formula, rn is 1 or more selected from the group consisting of Li, na, and K) is a component that can improve the meltability of the glass, but when contained in excess, it causes deterioration of the devitrification resistance at the time of processing. By improving the meltability of the glass, glass with good productivity can be obtained. Thus Rn 2 The upper limit of the sum of the contents of the O components is preferably 10.0% or less, more preferably 8.0%Hereinafter, it is more preferably 5.0% or less, still more preferably 3.0% or less, still more preferably 1% or less, still more preferably 0.8% or less. On the other hand, rn 2 The lower limit of the sum of the contents of the O components is preferably set to be greater than 0%, more preferably to be 0.1% or more, still more preferably to be 0.2% or more, still more preferably to be 0.3% or more, and still more preferably to be 0.4% or more.
The RO component (wherein R is at least one selected from the group consisting of Mg, ca, sr, ba) is a component which improves glass stability, but when contained in an excessive amount, it causes a decrease in refractive index. Therefore, the upper limit of the sum of the RO component contents is 10.0% or less, more preferably 8.0% or less, still more preferably 7.0% or less, still more preferably 6.0% or less, still more preferably 5.0% or less, still more preferably 4.0% or less, still more preferably 3.0% or less, still more preferably 2.0% or less, still more preferably 1.0% or less.
By mixing SiO 2 Component B 2 O 3 Total content of ingredients relative to TiO 2 Component, zrO 2 Component, nb 2 O 5 Molar ratio of total content of the components (SiO 2 +B 2 O 3 )/(TiO 2 +ZrO 2 +Nb 2 O 5 ) When the refractive index is 0.80 or less, a desired refractive index can be obtained while suppressing an increase in specific gravity. Thus, the molar ratio (SiO 2 +B 2 O 3 )/(TiO 2 +ZrO 2 +Nb 2 O 5 ) The upper limit of (2) is preferably 0.80 or less, more preferably 0.79 or less, and still more preferably 0.78 or less. On the other hand, molar ratio (SiO 2 +B 2 O 3 )/(TiO 2 +ZrO 2 +Nb 2 O 5 ) The lower limit of (2) is preferably greater than 0, more preferably 0.10 or more, still more preferably 0.15 or more, still more preferably 0.20 or more, still more preferably 0.25 or more, still more preferably 0.30 or more.
By mixing SiO 2 Component B 2 O 3 Total content of components relative to Ln 2 O 3 Total content of ingredientsMolar ratio (SiO) 2 +B 2 O 3 )/Ln 2 O 3 When the amount is 1.01 or more, deterioration of devitrification resistance can be suppressed. Thus, the molar ratio (SiO 2 +B 2 O 3 )/Ln 2 O 3 The lower limit of (2) is preferably 1.01 or more, more preferably 1.02 or more, still more preferably 1.03 or more, and still more preferably 1.04 or more. On the other hand, by mixing the molar ratio (SiO 2 +B 2 O 3 )/Ln 2 O 3 When the refractive index is 2.00 or less, the transmittance can be improved while the desired refractive index can be obtained. Thus, the molar ratio (SiO 2 +B 2 O 3 )/Ln 2 O 3 The upper limit of (2) is preferably 2.00 or less, more preferably 1.95 or less, further preferably 1.90 or less, further preferably 1.85 or less.
By adding Nb to 2 O 5 The composition is relative to TiO 2 Component, nb 2 O 5 Ingredients, WO 3 Component, bi 2 O 3 Molar ratio of total content of components Nb 2 O 5 /(TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 ) The refractive index can be increased by 0.10 or more. Nb (Nb) 2 O 5 The component is TiO 2 Ingredients, WO 3 Component, bi 2 O 3 Of the high refractive index components of the component, the component that can most improve the refractive index. By adjusting the total amount of the high refractive index component and Nb 2 O 5 The content of the component (A) can increase the refractive index while suppressing coloring of the glass. Thus, the molar ratio Nb 2 O 5 /(TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 ) The lower limit of (2) is preferably 0.10 or more, more preferably 0.11 or more, and still more preferably 0.12 or more. On the other hand, from the viewpoint of suppressing devitrification and coloration due to excessive content, the molar ratio Nb 2 O 5 /(TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 ) Preferably 0.30 or less, more preferably 0.25 or less, and even more preferably 0.23 or less.
By making Y 2 O 3 Composition of the componentsRelative to Ln 2 O 3 Molar ratio Y of the total content of the components 2 O 3 /Ln 2 O 3 The specific gravity of the glass can be reduced by 0.05 or more. Due to Y 2 O 3 The component is a component with smaller specific gravity in other rare earth oxides, so by adjusting the rare earth oxide and Y 2 O 3 The ratio of the components can obtain the effect of improving the refractive index while suppressing coloring. Thus, molar ratio Y 2 O 3 /Ln 2 O 3 The lower limit of (2) is preferably 0.05 or more, more preferably 0.07 or more, still more preferably 0.10 or more, and still more preferably 0.13 or more.
< concerning the component to be not contained >
Next, the components not to be contained in the optical glass of the present invention will be described.
Other components may be added as necessary within a range not to impair the characteristics of the glass of the present invention. However, in addition to Ti, zr, nb, W, la, gd, Y, yb, lu, since various transition metal components such as Nd, V, cr, mn, fe, co, ni, cu, ag and Mo have properties such that glass is colored and absorbed at a specific wavelength in the visible region even when they are contained in a small amount alone or in a small amount by being combined, it is preferable that the transition metal components are not substantially contained in the optical glass particularly in the wavelength in the visible region.
In addition, lead compounds such As PbO and As 2 O 3 The arsenic compound is an environmentally high-load component, and therefore is preferably substantially not contained, that is, not contained at all except for unavoidable contamination.
Further, in recent years, each component of Th, cd, tl, os, be and Se has a tendency to be used as a harmful chemical substance in a controlled manner, and it is necessary to take environmental protection measures not only in the glass manufacturing process but also in the processing process and disposal after production. Therefore, when environmental impact is important, it is preferable that these components are substantially absent.
Physical Properties
Refractive index (n) of the optical glass of the present invention d ) The lower limit of (2) is preferably 1.98000 or more, more preferably 1.99000 or more, and even more preferably 2.00000 or more. On the other hand, the refractive index (n d ) Preferably 2.50000 or less, more preferably 2.30000 or less, further preferably 2.20000 or less, further preferably 2.10000 or less.
Abbe number (v) of the optical glass of the present invention d ) The lower limit of (2) is preferably 18.00 or more, more preferably 20.00 or more, and even more preferably 23.00 or more. On the other hand, abbe number (v) of the optical glass of the present invention d ) The upper limit of (2) is preferably less than 35.00, more preferably 33.00 or less, and even more preferably 30.00 or less.
The glass of the present invention is preferably less colored. In particular, when the glass of the present invention is represented by the transmittance of glass, a sample having a thickness of 10mm exhibits a wavelength (lambda) of 70% of spectral transmittance 70 ) The upper limit of (2) is preferably 480nm or less, more preferably 470nm or less, still more preferably 460nm or less, and still more preferably 450nm or less. In addition, a wavelength (λ) exhibiting a spectral transmittance of 5% 5 ) The upper limit of (2) is preferably 390nm or less, more preferably 385nm or less, and even more preferably 380nm or less.
Optical glass having a high refractive index and a good transmittance is used for various applications such as cameras, imaging devices, optical devices including augmented reality devices and virtual reality devices. Therefore, the optical glass of the present invention has high versatility.
The specific gravity (d) of the optical glass of the present invention is preferably 5.50 or less, 5.40 or less, 5.30 or less, 5.20 or less, and 5.10 or less in this order.
By reducing the specific gravity, the glass becomes light, and thus the weight of the optical device can be reduced.
The upper limit of the liquidus temperature of the optical glass of the present invention is preferably 1250 ℃ or lower, more preferably 1230 ℃ or lower, and even more preferably 1210 ℃ or lower.
By lowering the liquidus temperature, a glass excellent in stability and productivity can be obtained.
[ method for producing optical glass ]
The optical glass of the present invention is not particularly limited, and can be produced, for example, as follows. That is, the above raw materials are uniformly mixed so that the respective components are within a predetermined content range, the prepared mixture is charged into a platinum crucible, melted in an electric furnace at a temperature range of 1100 to 1500 ℃ for 2 to 5 hours according to the melting difficulty of the glass raw materials, stirred and homogenized, cooled to a suitable temperature, and then cast into a mold, and slowly cooled to prepare the glass crucible. The reducing agent and the defoaming agent may be suitably used together with the glass raw materials.
[ shaping of glass ]
The optical glass of the present invention can be melt-molded by a known method. The means for molding the glass melt is not limited.
[ optical element ]
The optical glass thus produced can be used to produce a glass molded article by polishing, or by press molding such as reheat press molding or precision press molding. That is, the glass molded body can be produced by mechanical processing such as grinding and polishing of the optical glass. The means for producing the glass molded product is not limited to these means.
As described above, the optical glass of the present invention is useful for various optical elements and optical designs, and can realize high-definition and high-precision imaging characteristics and projection characteristics when used in optical devices such as cameras and projectors. In addition, the light guide plate used as a constituent member of an image display device such as Augmented Reality (AR), virtual Reality (VR), and Mixed Reality (MR) can realize a wide viewing angle and high brightness.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
The compositions of examples and comparative examples of the glasses of the present invention were used to obtain refractive indices (n d ) Abbe number (v) d ) Spectral transmittance shows wavelengths (lambda) of 5% and 70% 5 、λ 70 ) Specific gravity (d)Liquidus temperatures are shown in Table 1.
The optical glass of the present invention is produced by selecting, as raw materials of each component, high-purity raw materials used in a usual optical glass such as oxides, hydroxides, carbonates, nitrates, sulfates, fluorides, metaphosphoric acid compounds, etc., weighing the raw materials so as to be the composition ratios of the respective examples shown in the table, uniformly mixing the raw materials, charging the raw materials into a platinum crucible, melting the raw materials in an electric furnace at a temperature range of 1100 to 1500 ℃ for 30 minutes to 2 hours according to the melting difficulty of the raw materials, stirring the raw materials, homogenizing the raw materials, and casting the homogenized raw materials into a mold or the like, and cooling the molded product slowly.
Refractive index (n) of glasses of examples and comparative examples d ) Abbe number (v) d ) According to JIS B7071-2: the measurement was performed by the V block method defined in 2018. Here, refractive index (n d ) Expressed as a measurement value of d-line (587.56 nm) with respect to helium lamp. In addition, regarding Abbe number (. Nu.) d ) Using the refractive index (n d ) And refractive index (n) with respect to F line (486.13 nm) of hydrogen lamp F ) Refractive index (n) relative to C line (656.27 nm) C ) Is defined by Abbe number (v d )＝[(n d -1)/(n F -n C )]The formula is calculated. These refractive indices (n d ) Abbe number (v) d ) The temperature was determined by measuring glass obtained by setting the slow cooling rate to-25 ℃/hr.
The transmittance of the glasses of examples and comparative examples was measured according to the Japanese optical glass industry Association standards (measuring method of the coloration degree of JOGIS02-2019 optical glass). In the present invention, the presence or absence of coloration and the degree of the glass are determined by measuring the transmittance of the glass. Specifically, for a face-to-face parallel polished article having a thickness of 10.+ -. 0.1mm, the spectral transmittance of 200 to 700nm was measured according to JIS Z8722, and lambda was obtained 70 (wavelength at 70% transmittance) and lambda 5 (wavelength at 5% transmittance).
The specific gravity in the glass of the examples is based on the glass produced by JISZ8807: the measurement method of the density and specific gravity of 2012 by the weighing method in a liquid.
Liquidus temperature of the glass of the examples is expressed: a glass sample in the form of a broken glass of 5cc was charged into a platinum crucible of 50ml in volume, and the glass was brought into a molten state at 1400 ℃, cooled to a predetermined temperature and kept for 1 hour, and immediately after the glass was taken out from the furnace and cooled, the glass surface and the inside of the glass were observed for the presence or absence of crystals, and the lowest temperature of the crystals was not observed. Here, the predetermined temperature at the time of cooling is a temperature of 1350 ℃ to 800 ℃ at every 10 ℃.
As shown in table 1, the refractive index (nd) of the glasses of the examples of the present invention was 1.98000 or more, more specifically 2.00000 or more, within the desired range.
Abbe number (v) of the glass of the embodiment of the invention d ) Are each 20.00 or more, more specifically 23.00 or more, and the Abbe number (. Nu) d ) Is 35.00 or less, more specifically 30.00 or less, within a desired range.
Wavelength (lambda) of glass of the embodiment of the invention 70 ) Are each 480nm or less, more specifically 460nm or less, and have a wavelength (. Lambda. 5 ) Is 390nm or less, more specifically 380nm or less, within a desired range.
On the other hand, the refractive index and transmittance of the glass of comparative example 1, which do not satisfy the claims, cannot be said to be sufficient values.
The specific gravity (d) of the glasses of the examples of the present invention is 5.50 or less, more specifically 5.10 or less, within a desired range.
The glass of the examples of the present invention is highly stable.
Therefore, it is apparent that the optical glass of the embodiment of the present invention is a glass having a high refractive index, and having a high transmittance and further having a high stability.
The present invention has been described in detail above for the purpose of illustration, but it is to be understood that the present embodiment is for the purpose of illustration only and that various modifications can be made by those skilled in the art without departing from the spirit and scope of the invention.
Claims (4)
1. An optical glass comprising, in mole% based on oxides:
La 2 O 3 the components are 15.0 to 30.0 percent,
ZnO is 0-8.0%,
the BaO component is0 to 10.0 percent,
Rn 2 the sum of the contents of O components is more than 0% and less than 10.0%, wherein Rn is more than 1 selected from the group consisting of Li, na and K,
molar ratio (SiO) 2 +B 2 O 3 )/(TiO 2 +ZrO 2 +Nb 2 O 5 ) Is not more than 0.80 of the total weight of the composition,
molar ratio (SiO) 2 +B 2 O 3 )/Ln 2 O 3 Is 1.01 to 2.00, wherein Ln is 1 or more selected from the group consisting of La, Y, gd, yb,
molar ratio Nb 2 O 5 /(TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 ) Is 0.10 or more.
2. An optical glass according to claim 1, wherein the refractive index (n d ) 1.98000.
3. An optical element comprising the optical glass of any one of claims 1 or 2.
4. An optical device provided with the optical element according to claim 3.
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| JP2022-124321 | 2022-08-03 | ||
| JP2022124321A JP2024021478A (en) | 2022-08-03 | 2022-08-03 | Optical glass and optical element |
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| CN (1) | CN117510064A (en) |
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