CN117865468A - Optical glass, prefabricated member and optical element - Google Patents
Optical glass, prefabricated member and optical element Download PDFInfo
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- CN117865468A CN117865468A CN202410208486.1A CN202410208486A CN117865468A CN 117865468 A CN117865468 A CN 117865468A CN 202410208486 A CN202410208486 A CN 202410208486A CN 117865468 A CN117865468 A CN 117865468A
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- 239000005304 optical glass Substances 0.000 title claims abstract description 131
- 230000003287 optical effect Effects 0.000 title claims abstract description 51
- 239000011521 glass Substances 0.000 claims description 160
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 5
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 5
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 5
- 150000002222 fluorine compounds Chemical group 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 238000004031 devitrification Methods 0.000 abstract description 39
- 229910021193 La 2 O 3 Inorganic materials 0.000 abstract description 11
- 238000013461 design Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 description 45
- 239000000203 mixture Substances 0.000 description 27
- 238000002834 transmittance Methods 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 21
- 238000000465 moulding Methods 0.000 description 21
- 230000009477 glass transition Effects 0.000 description 19
- 239000000463 material Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 230000005484 gravity Effects 0.000 description 12
- 239000007791 liquid phase Substances 0.000 description 12
- 239000006060 molten glass Substances 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910018068 Li 2 O Inorganic materials 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 238000010186 staining Methods 0.000 description 4
- YEESUBCSWGVPCE-UHFFFAOYSA-N azanylidyneoxidanium iron(2+) pentacyanide Chemical compound [Fe++].[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.N#[O+] YEESUBCSWGVPCE-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 229960002460 nitroprusside Drugs 0.000 description 3
- 229910016569 AlF 3 Inorganic materials 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- 229910005690 GdF 3 Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical class OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 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
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 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
- 238000005303 weighing Methods 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
-
- 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
-
- 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
- C03C2203/00—Production processes
- C03C2203/10—Melting processes
Abstract
The invention can obtain a refractive index (n) d ) Abbe number (v) d ) All of which are within the required range and have high devitrification resistance. The optical glass contains, in mol%, B 2 O 3 5.0% to 55.0% of La 2 O 3 The content of the component (A) is 5.0% to 30.0%, and the sum of the moles (Nb) 2 O 5 +WO 3 ) Less than 10.0% and has a refractive index (n) of 1.70 or more d ) An Abbe number (v) of 25 to 50 d ). The optical glass can be used for various optical elements and optical designs.
Description
Technical Field
The invention relates to an optical glass, a prefabricated member and an optical element.
Background
In recent years, the digitization and high definition of devices using optical systems have been rapidly advanced, and in the field of various optical devices such as photographic equipment such as digital cameras and video cameras, and video playback (projection) devices such as projectors and projection televisions, there has been an increasing demand for reducing the number of optical elements such as lenses and prisms used in optical systems, and for reducing the weight and size of the entire optical systems.
In particular, an optical glass for manufacturing an optical element has a refractive index (n) of 1.70 or more, which enables the weight and size of the entire optical system to be reduced d ) And an Abbe number (v) of 25 to 50 inclusive d ) The demand for high refractive index low dispersion glass becomes very high. As such a glass having a high refractive index and low dispersion, glass components as described in patent documents 1 to 8 are widely known.
Japanese patent document laid-open No. 2011-178571
Japanese patent document No. 2014-047099
Japanese patent document No. 2013-067558
Japanese patent document Kokai 2012-214350 (Japanese patent document 4)
Japanese patent document No. 2011-093781
Japanese patent document No. 2009-203155
Japanese patent document No. 2011-173783
Japanese patent document No. 2011-225383
Technical problem to be solved by the invention
As a method for manufacturing an optical element from an optical glass, the following method is known: for example, a method of grinding and polishing a gob or a glass gob formed of an optical glass to obtain the shape of an optical element; a method of grinding and polishing a glass molded body obtained by performing reheat molding (reheat press molding) on a gob or a glass gob formed of an optical glass; and a method of molding (precision press molding) a preform obtained from a gob or a glass gob in an ultra-precision mold to obtain the shape of an optical element. In either method, it is required that a stable glass can be obtained when gobs or glass gobs are formed from a molten glass raw material. Here, when the stability against devitrification (devitrification resistance) of the glass constituting the obtained gob or glass block is lowered to form crystals inside the glass, the glass suitable as an optical element has not been obtained.
In addition, in order to reduce the material cost of the optical glass, it is required that the raw material cost of each component constituting the optical glass is as low as possible. In addition, in mass production of optical glass, it is required that devitrification is not easily generated in glass production. However, the glass compositions described in patent documents 1 to 8 are difficult to sufficiently satisfy these various requirements.
The present invention has been made in view of the above problems, and an object thereof is to obtain a refractive index (n d ) Abbe number (v) d ) All of which are within the required range and have high devitrification resistance.
Disclosure of Invention
As a result of repeated intensive experiments and studies to solve the above problems, the present inventors have found that B is contained 2 O 3 Composition and La 2 O 3 Refractive index (n) d ) Abbe number (v) d ) Within the required range and make the materialThe content of the components with higher material cost is reduced, in particular Nb 2 O 5 Ingredients and WO 3 The content of the components is reduced, and the liquid phase temperature of the glass is also lowered, thereby completing the present invention.
Specifically, the present invention provides an optical glass as described below.
(1) An optical glass characterized by comprising, in mol%, B 2 O 3 5.0% to 55.0% of La 2 O 3 The content of the component (A) is 5.0% to 30.0%, and the sum of the moles (Nb) 2 O 5 +WO 3 ) Less than 10.0%, and has a refractive index (n) d ) And an Abbe number (v) of 25 to 50 inclusive d )。
(2) The optical glass according to the above (1), which has a refractive index (n) d ) And an Abbe number (v) of 25 to 48 d )。
(3) The optical glass according to the above (1) or (2), which has a refractive index (n) of 1.70 to 1.90 d ) And an Abbe number (v) of 30 to 50 inclusive d )。
(4) The optical glass according to any one of the above (1) to (3), wherein the total amount of at least one component selected from the group consisting of CaO component and BaO component is more than 0% and less than 30.0% in mol%.
(5) The optical glass according to any one of the claims (1) to (4), wherein the glass is produced by a process comprising the steps of, in mol%,
SiO 2 the components are 0 to 25.0 percent,
ZnO is 0-45.0%,
ZrO 2 the components are 0 to 15.0 percent.
(6) The optical glass according to the above (1), wherein the glass is produced by, in mol%,
Nb 2 O 5 the components are 0 to less than 10.0 percent,
WO 3 the components are 0 to less than 10.0 percent,
Gd 2 O 3 the components are 0 to less than 4.0 percent,
Yb 2 O 3 the components are 0 to less than 4.0 percent
Ta 2 O 5 The components are 0 to less than 5.0 percent,
TiO 2 the components are 0 to less than 40.0 percent,
Y 2 O 3 The components are 0 to 25.0 percent,
MgO component is 0-10.0%,
the CaO component is 0 to 10.0 percent,
the SrO component is 0 to 10.0 percent,
the BaO component is 0 to 25.0 percent,
Li 2 the O component is 0 to 10.0 percent,
Na 2 the O component is 0 to 10.0 percent,
K 2 the O component is 0 to 10.0 percent,
P 2 O 5 the components are 0 to 10.0 percent,
GeO 2 the components are 0 to 10.0 percent,
Al 2 O 3 the components are 0 to 15.0 percent,
Ga 2 O 3 the components are 0 to 15.0 percent,
Bi 2 O 3 the components are 0 to 15.0 percent,
TeO 2 the components are 0 to 15.0 percent,
SnO 2 the components are 0 to 3.0 percent,
Sb 2 O 3 the components are 0 to 1.0 percent,
the content of F in the fluoride substituted with part or all of the oxide of one or more of the above metal elements is 0 to 15.0 mol%.
(7) The optical glass according to the above (1), wherein the molar ratio SiO 2 /B 2 O 3 Is 0.13 to 1.70 inclusive.
(8) The optical glass according to the above (1), wherein the sum of moles Ta 2 O 5 +Nb 2 O 5 +WO 3 +Gd 2 O 3 +Yb 2 O 3 Less than 10.0%.
(9) The optical glass according to the above (1), wherein the molar ratio ZnO/(La) 2 O 3 +Y 2 O 3 ) Is 0.10 to 4.00 inclusive.
(10) The optical glass according to the above (1), wherein Ln 2 O 3 The sum of the moles of the components is 5.0% or more and 40.0% or less, wherein Ln is 1 or more selected from the group consisting of La, gd, Y, yb, lu, and the sum of the moles of the RO components is 25.0% or less, wherein R is 1 or more selected from the group consisting of Mg, ca, sr, ba, and Rn 2 The sum of the moles of the O components is 10.0% or less, wherein Rn is 1 or more selected from the group consisting of Li, na and K.
(11) The optical glass according to the above (1), wherein the molar ratio (RO+ZnO)/Ln 2 O 3 More than 0.30, wherein R is 1 or more selected from the group consisting of Mg, ca, sr, ba, and Ln is 1 or more selected from the group consisting of La, gd, Y, yb, lu.
(12) A preform composed of the optical glass according to any one of the above (1) to (11).
(13) An optical element composed of the optical glass according to any one of the above (1) to (11).
(14) An optical device comprising the optical element according to (12) or (13).
Effects of the invention
According to the present invention, a refractive index (n d ) Abbe number (v) d ) All of which are within the required range and have high devitrification resistance.
Detailed Description
The optical glass of the present invention contains B in mol% 2 O 3 5.0% to 55.0% of La 2 O 3 The content of the component (A) is 5.0% to 30.0%, and the sum of the moles (Nb) 2 O 5 +WO 3 ) Less than 10.0%, has a refractive index (n) of 1.70 or more d ) An Abbe number (v) of 25 to 50 d )。
By mixing B with 2 O 3 Composition and La 2 O 3 The component (c) is particularly easy to obtain a substrate component having a refractive index (n) d ) And an Abbe number (v) of 25 to 50 inclusive d ) Is a stable glass of (a). In addition, the inventors of the present application found that, in particular, the refractive index (n) d ) And an Abbe number (v) of 25 to 50 inclusive d ) Even in the case of the glass with a high content of components which reduce the material cost, in particular Nb 2 O 5 Ingredients and WO 3 Even in the case of the content of the component, the liquid phase temperature of the glass can be reduced, and in particular, devitrification in the production of the glass can be reduced. Accordingly, a refractive index (n d ) Abbe number (v) d ) All of which are within the required range and have high devitrification resistance.
In addition, the optical glass of the present invention can be preferably used for transmitting visible light because of its high transmittance for visible light.
Among them, an optical glass having a refractive index (nd) of 1.75 or more and an abbe number (vd) of 25 or more and 48 or less may be used as the first optical glass. An optical glass having a refractive index (nd) of 1.70 to 1.90 and an abbe number (vd) of 30 to 50 may be used as the second optical glass.
The third optical glass may be an optical glass containing at least one of a CaO component and a BaO component, and having a total amount of more than 0% and less than 30.0%. By containing at least one of CaO component and BaO component, a refractive index (n) of 1.70 or more can be easily obtained d ) And an Abbe number (v) of 25 to 50 inclusive d ) And a more stable glass. In addition, particularly, by containing at least one of the CaO component and the BaO component, not only a desired high refractive index can be obtained, but also the transmittance to the short wavelength side of visible light can be improved. In addition to Nb 2 O 5 Ingredients and WO 3 In addition to the components, the total amount of the rare earth components can be reducedThe cost is reduced.
Embodiments of the optical glass of the present invention will be described in detail below. 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 will be omitted appropriately, the gist of the 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 oxide-converted composition. The term "oxide conversion composition" as used herein means a composition of each component contained in the glass, assuming that all of the oxides, complex salts, metal fluorides, and the like used as raw materials of the glass composition component of the present invention are decomposed and converted into oxides at the time of melting, the total mole number of the oxides is taken as 100 mole%.
< essential component, optional component >
B 2 O 3 The component (b) is a component necessary for forming an oxide as a glass in the optical glass of the present invention containing a large amount of rare earth oxide. In particular, by making B 2 O 3 The content of the component (A) is 5.0% or more, and the devitrification resistance of the glass can be improved, and the Abbe number of the glass can also be increased. Thus B 2 O 3 The content of the component (a) is preferably 5.0% or more, more preferably 10.0% or more, still more preferably 14.0% or more, still more preferably 15.0% or more, still more preferably 19.0% or more, still more preferably 20.0% or more, and still more preferably 25.0% or more.
On the other hand, by making B 2 O 3 The content of the component is 55.0% or less, a larger refractive index can be obtained relatively easily, and a decrease in chemical durability can also be suppressed. Thus B 2 O 3 Composition of the componentsThe content of (2) is preferably 55.0% or less, more preferably less than 51.0%, even more preferably 50.0% or less, even more preferably less than 47.0%, even more preferably less than 45.0%, even more preferably less than 42.0%, even more preferably less than 40.0%, even more preferably less than 38.0%.
B 2 O 3 As the component (A), H can be used as a raw material 3 BO 3 、Na 2 B 4 O 7 、Na 2 B 4 O 7 ·10H 2 O、BPO 4 Etc.
La 2 O 3 The component (A) is an essential component capable of increasing the refractive index of the glass. Therefore La 2 O 3 The content of the component (A) is preferably 5.0% or more, more preferably 7.0% or more, still more preferably 8.0% or more, and still more preferably 10.0% or more.
On the other hand, by making La 2 O 3 The content of the component is 30.0% or less, whereby the glass stability can be improved to reduce devitrification, and also an excessive increase in Abbe number can be suppressed. In addition, the meltability of the glass raw material can be improved. Therefore La 2 O 3 The content of the component (A) is preferably 30.0% or less, more preferably less than 25.0%, even more preferably less than 22.0%, even more preferably less than 21.0%, even more preferably less than 20.0%, even more preferably 19.5% or less, even more preferably 17.5% or less, even more preferably 16.5% or less, and even more preferably 14.5% or less.
La 2 O 3 La can be used as a raw material of the component 2 O 3 、La(NO 3 ) 3 ·XH 2 O (X is an arbitrary integer), and the like.
Nb 2 O 5 Ingredients and WO 3 The total amount of the components is preferably less than 10.0%. Accordingly, the content of these more expensive components is reduced, so that the material cost of the glass can be reduced. Thus, the sum of moles (Nb) 2 O 5 +WO 3 ) Preferably less than 10.0%, more preferably less than 5.0%, and still more preferablyMore preferably, the content is less than 3.0%, still more preferably less than 2.0%, still more preferably less than 1.5%, still more preferably less than 1.0%, still more preferably less than 0.5%, still more preferably less than 0.1%.
Preferably, at least one of CaO component and BaO component is contained in a total amount of 0% to 30.0%.
In particular, by making the sum larger than 0%, the refractive index of the glass and the transmittance of visible light can be improved. In addition, the content of the rare earth component can be reduced, so that the cost can be further reduced. Therefore, the sum of the moles (CaO+BaO) is preferably more than 0%, more preferably more than 1.0%, and still more preferably more than 2.0%.
On the other hand, when the sum is 30.0% or less, the liquid phase temperature of the glass can be reduced, and thus devitrification of the glass can be reduced. Therefore, the sum of the mol (CaO+BaO) is preferably 30.0% or less, more preferably less than 25.0%, still more preferably less than 20.0%, and still more preferably less than 15.0%.
SiO 2 When the content exceeds 0%, the viscosity of the molten glass can be increased, and the dyeing of the glass can be reduced. In addition, the stability of the glass is improved, and the glass suitable for mass production is easily produced. Thus, siO 2 The content of the component (A) is preferably more than 0%, more preferably more than 1.0%, even more preferably more than 5.0%, even more preferably more than 8.0%, even more preferably more than 10.2%, and even more preferably more than 10.5%.
On the other hand, by making SiO 2 The content of the component is 25.0% or less, and the rise in glass transition temperature and the decrease in refractive index can be suppressed. Thus, siO 2 The content of the component (A) is preferably 25.0%, more preferably less than 22.0%, even more preferably less than 20.0%, even more preferably less than 18.0%, even more preferably less than 15.5%, and even more preferably less than 14.0%.
SiO 2 As the component, siO can be used as a raw material 2 、K 2 SiF 6 、Na 2 SiF 6 Etc.
The ZnO component is any component that, when the content exceeds 0%, can improve the meltability of the raw material, promote the degassing of molten glass, and can improve the glass stability. In addition, the glass may be dyed with an arbitrary component that can be reduced by shortening the melting time or the like. In addition, it is also an arbitrary component that can lower the glass transition temperature and can improve chemical durability. Accordingly, the content of the ZnO component is preferably more than 0%, more preferably more than 1.0%, even more preferably more than 2.2%, even more preferably more than 2.5%, even more preferably more than 4.2%, even more preferably more than 4.5%, even more preferably more than 5.0%, even more preferably more than 5.5%, even more preferably more than 6.5%, even more preferably more than 8.5%, even more preferably more than 10.0%, and even more preferably more than 15.0%.
On the other hand, by setting the content of the ZnO component to 45.0% or less, it is possible to suppress a decrease in refractive index of the glass and also to reduce devitrification due to an excessive decrease in viscosity. Accordingly, the content of the ZnO component is preferably 45.0% or less, more preferably less than 40.0%, even more preferably less than 35.0%, even more preferably less than 33.0%, and even more preferably less than 32.0%.
As the ZnO component, znO and ZnF can be used as raw materials 2 Etc.
ZrO 2 When the content exceeds 0%, the refractive index and Abbe number of the glass can be increased, and the devitrification resistance can be improved. Thus, zrO 2 The content of the component (A) is preferably more than 0%, more preferably more than 1.0%, even more preferably more than 2.0%, and still more preferably more than 2.0%.
On the other hand, by making ZrO 2 The content of the component (A) is 15.0% or less, and ZrO can be reduced 2 Devitrification caused by excessive content of the components. Thus, zrO 2 The content of the component (A) is preferably 15.0% or less, more preferably less than 12.0%, and still more preferablyDesirably less than 10.0%, more desirably less than 6.9%, and even more desirably less than 6.0%.
ZrO 2 As the component (A), zrO can be used as the raw material 2 、ZrF 4 Etc.
Nb 2 O 5 The component (A) is any component that can increase the refractive index of the glass and can increase the devitrification resistance by lowering the liquidus temperature of the glass when the content exceeds 0%.
On the other hand, by making Nb 2 O 5 The content of the components is less than 10.0%, and the material cost of the glass can be controlled. In addition, due to Nb can be reduced 2 O 5 Devitrification caused by excessive content of the component can also be suppressed, and a decrease in transmittance of the glass to visible light (particularly, wavelength 500nm or less) can be suppressed. In addition, the reduction in abbe number can be suppressed accordingly. Thus, nb 2 O 5 The content of the component (A) is preferably less than 10.0%, more preferably less than 5.0%, even more preferably less than 3.0%, even more preferably less than 2.0%, even more preferably less than 1.4%, even more preferably less than 1.0%, even more preferably less than 0.5%, even more preferably less than 0.1%. In particular, from the viewpoint of reducing the material cost, it is most preferable that Nb is not contained 2 O 5 The components are as follows.
Nb 2 O 5 The component (A) may be Nb 2 O 5 Etc.
WO 3 When the content exceeds 0%, the glass may be dyed with other high refractive index components, the refractive index may be increased, the glass transition temperature may be lowered, and the devitrification resistance may be improved.
On the other hand, by making WO 3 The content of the components is less than 10.0%, and the material cost of the glass can be controlled. In addition, by reducing the number of steps from WO 3 The composition causes staining of the glass to increase the transmittance of visible light. Thus, WO 3 The content of the component (A) is preferably less than 10.0%, more preferably less than 5.0%, still more preferably less than 3.0%, and still more preferablyLess than 1.0%, more preferably less than 0.5%, and still more preferably less than 0.1%. In particular, from the viewpoint of reducing the cost of materials, it is most preferable not to contain WO 3 The components are as follows.
WO 3 As the component (A), WO can be used as a raw material 3 Etc.
Gd 2 O 3 Composition and Yb 2 O 3 The component (A) is any component that can increase the refractive index of the glass when the content exceeds 0%.
However, due to Gd 2 O 3 Composition and Yb 2 O 3 The raw materials of the components are more expensive, and if the content is more, the production cost is increased, so that the reduction of Nb can be reduced 2 O 5 Ingredients and WO 3 Components, etc. In addition, by reducing Gd 2 O 3 Composition and Yb 2 O 3 The content of the components can suppress the increase in Abbe number of the glass. Thus Gd 2 O 3 Composition and Yb 2 O 3 The content of each component is preferably less than 4.0%, more preferably less than 2.0%, even more preferably less than 1.0%, even more preferably less than 0.5%, and even more preferably less than 0.1%. In particular, it is desirable that these components are not contained in view of reducing the material cost.
Gd 2 O 3 Composition and Yb 2 O 3 Gd can be used as a raw material of the component 2 O 3 、GdF 3 、Yb 2 O 3 Etc.
Ta 2 O 5 When the content exceeds 0%, the refractive index and the devitrification resistance of the glass can be improved.
However, due to Ta 2 O 5 The raw materials of the components are more expensive, and if the amount is more, the production cost increases, so that the reduction of Nb can be reduced 2 O 5 Ingredients and WO 3 Components, etc. In addition, since Ta is used as a catalyst 2 O 5 The content of the components is less than 5.0%, so that the melting temperature of the raw material isThe energy required for melting the raw material is reduced, and thus the manufacturing cost of the optical glass can be reduced. Thus, ta 2 O 5 The content of the component (A) is preferably less than 5.0%, more preferably less than 3.0%, even more preferably less than 1.0%, even more preferably less than 0.5%, and even more preferably less than 0.1%. In particular, from the viewpoint of reducing the material cost, it is most preferable that Ta is not contained 2 O 5 The components are as follows.
Ta 2 O 5 As the component, ta may be used as a raw material 2 O 5 Etc.
TiO 2 The component (A) is any component that can increase the refractive index of the glass and improve the stability by lowering the liquidus temperature of the glass when the content exceeds 0%. Thus, tiO 2 The content of the component (A) is preferably more than 0%, more preferably more than 1.1%, even more preferably more than 4.0%, even more preferably more than 5.0%, and still even more preferably more than 6.5%.
On the other hand, by making TiO 2 The content of the component is less than 40.0%, and the content of TiO is reduced 2 Devitrification caused by excessive content of the component can also be suppressed, and a decrease in transmittance of the glass to visible light (particularly, wavelength 500nm or less) can be suppressed. In addition, the reduction in abbe number can be suppressed accordingly. Thus, tiO 2 The content of the component (A) is preferably less than 40.0%, more preferably less than 37.0%, even more preferably less than 35.0%, even more preferably less than 30.0%, even more preferably less than 26.0%, even more preferably less than 25.0%, even more preferably less than 23.0%, even more preferably less than 20.0%, and even more preferably less than 15.0%.
TiO 2 The component (A) may be TiO 2 Etc.
Y 2 O 3 When the content exceeds 0%, the glass composition can be used as an arbitrary composition which can maintain a high refractive index and a high Abbe number as compared with other rare earth elements, can control the material cost of the glass, and can reduce the specific gravity of the glass as compared with other rare earth elements. Thus Y 2 O 3 The content of the component (A) is preferably more than 0%, more preferably more than 1.0%, even more preferably more than 1.5%, and still more preferably more than 2.0%.
On the other hand, by making Y 2 O 3 The content of the component is 25.0% or less, and the reduction of the refractive index of the glass can be suppressed, and the stability of the glass can be improved. In addition, the decrease in the meltability of the glass raw material can be suppressed. Thus Y 2 O 3 The content of the component (A) is preferably 25.0% or less, more preferably less than 20.0%, even more preferably less than 10.0%, even more preferably less than 8.0%, and even more preferably less than 7.0%.
Y 2 O 3 The component (A) may be Y 2 O 3 、YF 3 Etc.
The MgO component, caO component, srO component and BaO component are arbitrary components whose refractive index, meltability and devitrification resistance of the glass can be adjusted when the content exceeds 0%. In particular, the BaO component is also a component that can improve the refractive index and the meltability of the glass raw material. Therefore, the content of the BaO component is preferably more than 0%, more preferably more than 1.0%, and still more preferably more than 2.0%.
On the other hand, by setting the content of the MgO component, caO component, and SrO component to 10.0% or less, it is possible to suppress a decrease in refractive index and also to reduce devitrification due to the inclusion of excessive amounts of these components. Accordingly, the content of the MgO component, the CaO component and the SrO component is preferably 10.0% or less, more preferably less than 5.0% or less, still more preferably less than 3.0% or less, and still more preferably less than 1.0% or less, respectively.
In addition, by setting the content of the BaO component to 25.0% or less, the desired refractive index can be obtained relatively easily, and devitrification due to the inclusion of excessive such components can be reduced. Therefore, the content of BaO component is preferably 25.0% or less, more preferably less than 20.0%, and still more preferably less than 15.0%.
MgO formationAs the components, caO component, srO component and BaO component, mgCO can be used as a raw material 3 、MgF 2 、CaCO 3 、CaF 2 、Sr(NO 3 ) 2 、SrF 2 、BaCO 3 、Ba(NO 3 ) 2 、BaF 2 Etc.
Li 2 O component, na 2 O component and K 2 The O component is any component that can improve the meltability of glass and can lower the glass transition temperature when the content exceeds 0%.
On the other hand, by making Li 2 O component, na 2 O component and K 2 The content of each of the O components is 10.0% or less, whereby the refractive index of the glass is hardly lowered and devitrification of the glass can be reduced. In addition, especially due to the reduction of Li 2 The content of the O component can improve the viscosity of the glass, so that the streaks of the glass can be reduced. Thus Li 2 O component, na 2 O component and K 2 The content of each of the O components is preferably 10.0% or less, more preferably less than 5.0%, even more preferably less than 3.0%, even more preferably less than 1.0%, even more preferably less than 0.5%, and even more preferably less than 0.1%.
Li 2 O component, na 2 O component and K 2 The O component may be Li as a raw material 2 CO 3 、LiNO 3 、Li 2 CO 3 、Na 2 CO 3 、NaNO 3 、NaF、Na 2 SiF 6 、K 2 CO 3 、KNO 3 、KF、KHF 2 、K 2 SiF 6 Etc.
P 2 O 5 When the content exceeds 0%, the glass may have a low liquidus temperature and may have an improved devitrification resistance.
On the other hand, by making P 2 O 5 The content of the component (A) is 10.0% or less, and the decrease in chemical durability, particularly water resistance, of the glass can be suppressed. Thus, P 2 O 5 The content of the component (A) is preferably 10.0% or less, more preferably less than 5.0%,more desirably less than 3.0%.
P 2 O 5 As the component (A), al (PO) can be used as a raw material 3 ) 3 、Ca(PO 3 ) 2 、Ba(PO 3 ) 2 、BPO 4 、H 3 PO 4 Etc.
GeO 2 When the content exceeds 0%, the refractive index of the glass can be increased, and the devitrification resistance can be improved.
However, due to GeO 2 The raw materials have high price, and if the content is high, the production cost is increased, so that the Gd reduction can be reduced 2 O 3 Composition and Ta 2 O 5 Components, etc. Thus, geO 2 The content of the component (A) is preferably 10.0% or less, more preferably less than 5.0%, even more preferably less than 3.0%, even more preferably less than 1.0%, and even more preferably less than 0.1%. From the viewpoint of reducing the material cost, geO may not be contained 2 The components are as follows.
GeO 2 As the component, geO can be used as the raw material 2 Etc.
Al 2 O 3 Composition and Ga 2 O 3 When the content exceeds 0%, the chemical durability of the glass and the devitrification resistance of the molten glass can be improved.
On the other hand, by making Al 2 O 3 Composition and Ga 2 O 3 The content of each component is 15.0% or less, and the glass can be reduced in liquid phase temperature and improved in devitrification resistance. Thus, al 2 O 3 Composition and Ga 2 O 3 The content of each component is preferably 15.0% or less, more preferably less than 10.0%, even more preferably less than 5.0%, and even more preferably less than 3.0%.
Al 2 O 3 Composition and Ga 2 O 3 As the component, al can be used as a raw material 2 O 3 、Al(OH) 3 、AlF 3 、Ga 2 O 3 、Ga(OH) 3 Etc.
Bi 2 O 3 The component (c) is any component that can increase the refractive index and reduce the glass transition temperature when the content exceeds 0%.
On the other hand, by making Bi 2 O 3 The content of the component (A) is 15.0% or less, and the glass can be reduced in liquidus temperature and improved in devitrification resistance. Therefore, bi 2 O 3 The content of the component (A) is preferably 15.0% or less, more preferably less than 10.0%, even more preferably less than 5.0%, even more preferably less than 3.0%, and even more preferably less than 1.0%.
Bi 2 O 3 Bi can be used as a raw material for the component (A) 2 O 3 Etc.
TeO 2 The component (c) is any component that can increase the refractive index and reduce the glass transition temperature when the content exceeds 0%.
On the other hand, teO 2 When a glass raw material is melted in a platinum crucible and a melting tank formed of platinum at a portion in contact with molten glass, there is a problem that the glass raw material can be alloyed with platinum. Thus, teO 2 The content of the component (A) is preferably 15.0% or less, more preferably less than 10.0%, even more preferably less than 5.0%, even more preferably less than 3.0%, and even more preferably less than 1.0%.
TeO 2 As the component (A), teO can be used as the raw material 2 Etc.
SnO 2 When the content exceeds 0%, the content of the component (A) is any component that can not only reduce oxidation of the molten glass to make it clear but also enhance the visible light transmittance of the glass.
On the other hand, by making SnO 2 The content of the component (A) is 3.0% or less, and the staining of the glass and devitrification of the glass due to the reduction of the molten glass can be reduced. In addition, since SnO can be reduced 2 Alloying of the components with the melting equipment (in particular, noble metals such as Pt) can thus achieve a longer service life of the melting equipment. Thus, snO 2 The content of the component (A) is preferably 3.0% or less, more preferably Less than 1.0%, more preferably less than 0.5%, still more preferably less than 0.1%.
SnO 2 As the component (A), snO and SnO can be used as raw materials 2 、SnF 2 、SnF 4 Etc.
Sb 2 O 3 The component (A) may be any component that can defoam the molten glass when the content exceeds 0%.
On the other hand, if Sb 2 O 3 An excessive amount may cause a decrease in transmittance in a short wavelength region of the visible light region. Thus, sb 2 O 3 The content of the component (A) is preferably 1.0% or less, more preferably less than 0.5%, and still more preferably less than 0.3%.
Sb 2 O 3 The component (b) may be Sb 2 O 3 、Sb 2 O 5 、Na 2 H 2 Sb 2 O 7 ·5H 2 O, etc.
In addition, the components for clearing and defoaming the glass are not limited to the above Sb 2 O 3 The components may be clarifying agents and deaerating agents well known in the art of glass manufacturing, or combinations thereof.
The F component is any component that can increase the Abbe number of the glass, lower the glass transition temperature, and improve the devitrification resistance when the content exceeds 0%.
However, if the total amount of F of the fluoride substituted with a part or all of the above-mentioned oxides of one or two or more metal elements exceeds 15.0%, the volatilization amount of the F component increases, and thus it is difficult to obtain a stable optical constant and a homogeneous glass. In addition, the abbe number excessively increases.
Accordingly, the content of the F component is preferably 15.0% or less, more preferably less than 10.0%, still more preferably less than 5.0%, and still more preferably less than 3.0%.
As the F component, for example, zrF can be used as a raw material 4 、AlF 3 、NaF、CaF 2 And the like, so as to be contained in glass.
Relative to B 2 O 3 Content of the component SiO 2 The ratio (molar ratio) of the content of the components is preferably 0.13 to 1.70.
In particular, by setting the molar ratio to 0.13 or more, devitrification can be reduced and stable glass suitable for mass production can be obtained relatively easily. Thus, molar ratio SiO 2 /B 2 O 3 Preferably, the ratio is 0.13 or more, more preferably 0.15 or more, still more preferably 0.17 or more, still more preferably 0.18 or more, still more preferably more than 0.20, still more preferably more than 0.24, still more preferably more than 0.28, still more preferably more than 0.32.
On the other hand, by setting the molar ratio to 1.70 or less, an increase in the glass transition temperature can be suppressed. Thus, molar ratio SiO 2 /B 2 O 3 Preferably 1.70 or less, more preferably 1.50 or less, still more preferably 1.30 or less, still more preferably less than 1.30, still more preferably less than 1.20, still more preferably less than 1.00, still more preferably less than 0.85, still more preferably less than 0.80, still more preferably less than 0.70.
Ta 2 O 5 Component, nb 2 O 5 Ingredients, WO 3 Component, gd 2 O 3 Composition and Yb 2 O 3 The total amount (sum of moles) of the components is preferably less than 10.0%. Accordingly, the material cost of the glass can be reduced due to the reduced content of these more expensive components. Thus, the sum of moles Ta 2 O 5 +Nb 2 O 5 +WO 3 +Gd 2 O 3 +Yb 2 O 3 Preferably less than 10.0%, more preferably less than 8.0%, even more preferably less than 5.0%, even more preferably less than 3.0%, even more preferably less than 2.0%, even more preferably less than 1.0%. In particular, from the viewpoint of obtaining a glass with a low material cost, it is more preferable to add Ta to the molar sum 2 O 5 +Nb 2 O 5 +WO 3 +Gd 2 O 3 +Yb 2 O 3 Less than 0.1%, most preferably 0%.
Relative to La 2 O 3 Component and Y 2 O 3 The ratio (molar ratio) of the content of the component(s) to the content of the ZnO component(s) is preferably 0.10 to 4.00.
In particular, when the molar ratio is 0.10 or more, the meltability of the glass raw material can be improved, and more stable glass can be easily obtained. Thus, the molar ratio ZnO/(La) 2 O 3 +Y 2 O 3 ) Preferably, the lower limit is 0.10, more preferably 0.15, even more preferably 0.20, even more preferably 0.24, even more preferably more than 0.26, even more preferably 0.27, even more preferably 0.32, even more preferably 0.35.
On the other hand, by making the molar ratio 4.00 or less, the liquid phase temperature can be reduced, and devitrification due to excessive decrease in the glass transition temperature can be reduced. Thus, the molar ratio ZnO/(La) 2 O 3 +Y 2 O 3 ) The upper limit is preferably 4.00, more preferably 3.50, even more preferably 3.00, and even more preferably 2.50.
Ln 2 O 3 The sum (molar sum) of the contents of the components (wherein Ln is one or more selected from the group consisting of La, gd, Y, yb, lu) is preferably 5.0% to 40.0%.
In particular, when the sum is 5.0% or more, the refractive index and abbe number of the glass can be increased, and thus a glass having a desired refractive index and abbe number can be obtained relatively easily. Thus Ln 2 O 3 The sum of the molar amounts of the components is preferably 5.0% or more, more preferably 8.0% or more, still more preferably 10.0% or more, still more preferably 11.0% or more, still more preferably 12.0% or more.
On the other hand, by setting the sum to 40.0% or less, the liquidus temperature of the glass can be reduced, and thus devitrification of the glass can be reduced. In addition, anotherIn addition, an excessive increase in the Abbe number can be suppressed. Thus Ln 2 O 3 The sum of the molar amounts of the components is preferably 40.0% or less, more preferably 35.0% or less, even more preferably 30.0% or less, more preferably 27.0% or less, even more preferably 25.0% or less, even more preferably 22.0% or less, even more preferably 20.0% or less, even more preferably 18.0% or less, and even more preferably 16.5% or less.
In particular, in the third optical glass, even Ln is obtained by containing at least one of CaO component and BaO component 2 O 3 The content of the components is smaller, and the glass with a desired high refractive index can be obtained, so that the material cost of the glass can be further reduced.
The sum (molar sum) of the contents of RO components (wherein R is 1 or more selected from the group consisting of Mg, ca, sr, ba) is preferably 25.0% or less. Accordingly, a decrease in refractive index can be suppressed, and the stability of the glass can be improved. Therefore, the sum of the mol% of the RO components is preferably 25.0% or less, more preferably less than 20.0%, and still more preferably less than 15.0%.
On the other hand, the sum of the mol% of the RO components is preferably more than 0%, more preferably more than 1.0%, and still more preferably more than 2.0%.
Rn 2 The sum (molar sum) of the contents of the O component (wherein Rn is 1 or more selected from the group consisting of Li, na and K) is preferably 10.0% or less. Accordingly, the reduction in viscosity of the molten glass can be suppressed, the refractive index of the glass is made difficult to be reduced, and devitrification of the glass can be reduced. Thus Rn 2 The molar sum of the O components is preferably 10.0% or less, more preferably less than 5.0%, still more preferably less than 3.0%, still more preferably less than 1.0%, still more preferably less than 0.5%, still more preferably less than 0.1%.
Relative to Ln 2 O 3 Wherein Ln is 1 or more selected from the group consisting of La, gd, Y, yb, lu, and RO component (wherein R isMore than 1 selected from the group consisting of Mg, ca, sr, ba) and the ratio (molar ratio) of the total content of ZnO components is preferably more than 0.30.
Accordingly, the material cost of the glass can be further reduced, and the stability of the glass can be improved. Thus, the molar ratio (RO+ZnO)/Ln 2 O 3 More preferably, the ratio is more than 0.30, still more preferably more than 0.45, still more preferably more than 0.50, still more preferably more than 0.80, still more preferably more than 1.00.
On the other hand, from the viewpoint of suppressing the decrease in refractive index, the molar ratio is preferably less than 7.00, more preferably less than 5.00, and even more preferably less than 4.00.
The ratio (molar ratio) of the content of the BaO component to the content of the ZnO component is preferably 5.00 or less. Accordingly, the meltability of the glass raw material and the stability of the glass can be improved. Therefore, the molar ratio BaO/ZnO is preferably 5.00 as an upper limit, more preferably 4.00 as an upper limit, even more preferably 3.00 as an upper limit, even more preferably 2.80 as an upper limit, and even more preferably 2.50 as an upper limit.
The content ratio (molar ratio) of the BaO component to the total content of RO components (wherein R is 1 or more selected from the group consisting of Mg, ca, sr, ba) is preferably 0.50 or more. Accordingly, the refractive index of the glass can be increased. Therefore, the molar ratio BaO/RO is preferably 0.50 as a lower limit, more preferably 0.70 as a lower limit, and even more preferably 0.80 as a lower limit.
The upper limit of the molar ratio may be 1.00.
< concerning the component that should not be contained >
Next, the components that should not be contained in the optical glass of the present invention, and preferable components are not contained.
The other components may be added as necessary within a range not to deteriorate the glass characteristics of the present invention. However, in addition to Ti, zr, nb, W, la, gd, Y, yb, lu, V, cr, mn, fe, co, ni, cu, ag and various transition metal components such as Mo have a characteristic that glass is stained and absorbs a specific wavelength in the visible region even when a small amount of each component is contained alone or in combination, and therefore, it is preferable that the glass is practically not contained in an optical glass using a wavelength in the visible region.
In addition, lead compounds such As PbO and As 2 O 3 The arsenic compound is a component with a high environmental load, and is preferably not substantially contained, that is, is preferably not uniformly contained except for unavoidable contamination.
In addition, in recent years, each component of Th, cd, tl, os, be and Se has a tendency to restrict its use as a harmful chemical, and environmental protection measures are required not only in the production process of glass but also in the treatment process and the treatment until after the production. Therefore, in the case where the influence on the environment is important, it is preferable that these components are not substantially contained.
[ method of production ]
The optical glass of the present invention is produced, for example, as follows. That is, in order to uniformly mix the above raw materials in a predetermined content range, the mixture thus produced is placed in a platinum crucible, melted for 2 to 5 hours in a temperature range of 1100 to 1500 ℃ by an electric furnace according to the melting difficulty of the glass raw materials, uniformly stirred, then cooled to an appropriate temperature, poured into a mold, and slowly cooled, thereby producing an optical glass.
In this case, it is preferable to use a material having high melting property as a glass raw material. Accordingly, since the glass can be melted at a lower temperature in a shorter time, the production efficiency of the glass can be improved and the production cost can be reduced. In addition, since volatilization of components and reaction with a crucible or the like can be reduced, glass with less staining can be obtained more easily.
[ physical Properties ]
The optical glass of the present invention preferably has a high refractive index and a high abbe number (low dispersion).
Refractive index (n) of the optical glass of the present invention d ) Ratio ofPreferably, the lower limit is 1.70, more preferably 1.72, even more preferably 1.74, even more preferably 1.75, even more preferably 1.78, and even more preferably 1.80. In particular, the refractive index (n d ) The lower limit is preferably 1.75, more preferably 1.78, still more preferably 1.79, and still more preferably 1.80.
On the other hand, the refractive index (n d ) The upper limit is preferably 2.10, more preferably 2.00, even more preferably 1.90, and even more preferably 1.85. In particular, the refractive index (n d ) The upper limit is preferably 1.90, more preferably 1.88, and even more preferably 1.85.
Abbe number (. Nu.) of the optical glass of the present invention d ) The lower limit is preferably 25, more preferably 27, even more preferably 28, even more preferably 30, and even more preferably 32.
On the other hand, the Abbe number (. Nu. d ) It is preferable that 50 be the upper limit, 48 be the upper limit, 45 be the upper limit, 43 be the upper limit, 42 be the upper limit, 41 be the upper limit, and 40.5 be the upper limit. In particular, the Abbe number (. Nu.) of the first optical glass d ) The upper limit is preferably 48, more preferably 45, even more preferably 43, and even more preferably 41.
Since the refractive index is high, a large refractive index of light can be obtained even when the optical element is required to be thin. In addition, since the dispersion is low, when the lens is used as a single lens, the shift of the focal point (chromatic aberration) due to the wavelength of light can be reduced. Therefore, for example, when an optical system is constituted by combining an optical element having high dispersion (low abbe number), aberration of the entire optical system can be reduced to obtain high imaging characteristics.
In this way, the optical glass of the present invention is useful for optical design, and particularly, when an optical system is configured, not only can high imaging characteristics and the like be realized and miniaturization of the optical system be achieved, but also the degree of freedom of optical design can be expanded.
The optical glass of the present invention is excellent in high devitrification resistance, and more specifically, low liquid phase temperature. That is, the liquid phase temperature of the optical glass of the present invention is preferably 1200℃as an upper limit, more preferably 1150℃as an upper limit, and even more preferably 1100 ℃. Accordingly, even if the molten glass flows out at a lower temperature, the degree of crystallization of the produced glass is reduced, so that devitrification at the time of forming the glass from a molten state can be reduced, and the influence on the optical characteristics of an optical element using the glass can be reduced. In addition, since glass can be molded even when the glass melting temperature is lowered, the glass manufacturing cost can be reduced by controlling the energy consumption at the time of glass molding. On the other hand, the lower limit of the liquid phase temperature of the optical glass of the present invention is not particularly limited, but the liquid phase temperature of the glass obtained by the present invention is substantially 800 ℃ or higher, specifically 850 ℃ or higher, more specifically 900 ℃ or higher. In the present invention, the "liquid phase temperature" means the minimum temperature at which 30cc of a glass sample in a broken glass state is added to a platinum crucible having a capacity of 50ml, the glass sample is completely melted at 1250 ℃, cooled to a desired temperature and kept for 1 hour, taken out from the furnace, immediately after cooling, the surface and the inside of the glass are observed for crystallization, and the presence or absence of crystallization is confirmed. The temperature required for cooling is a temperature of 1200 to 800 ℃ at 10 ℃ intervals.
The optical glass has higher visible light transmittance, particularly the transmittance of the side light with the short wavelength in the visible light, and is better in dyeing.
In the optical glass of the present invention, the spectral transmittance showed a wavelength (λ) of 80% in a sample having a thickness of 10mm 80 ) Preferably at 55The upper limit is 0nm, more preferably 520nm, and still more preferably 500 nm.
In the optical glass of the present invention, the spectral transmittance showed a wavelength (λ) of 70% in a sample having a thickness of 10mm 70 ) The upper limit is preferably 500nm, more preferably 450nm, even more preferably 420nm, and even more preferably 400 nm.
In the optical glass of the present invention, the spectral transmittance showed the shortest wavelength of 5% (lambda 5 ) The upper limit is preferably 400nm, more preferably 380nm, and still more preferably 360 nm.
Accordingly, since the absorption edge of the glass is located in or near the ultraviolet region, the transparency of the glass to visible light is improved, and therefore the optical glass can be preferably used for an optical element such as a lens that transmits light.
The optical glass of the present invention preferably has a glass transition temperature (Tg) of 700 ℃ or lower.
Accordingly, since the optical glass has a glass transition temperature of 700 ℃ or lower and can be softened at a lower temperature, even when the optical glass is used for press molding, press molding of the glass can be performed at a lower temperature more easily. Therefore, the glass transition temperature of the optical glass of the present invention is preferably 700℃or lower, more preferably 650℃or lower, and even more preferably 630℃or lower.
On the other hand, the glass transition temperature of the optical glass may be 500℃or higher. Accordingly, since crystallization is hardly caused by improving the stability of the glass, devitrification at the time of manufacturing the glass or at the time of press molding can be reduced, and thus a glass more suitable for press molding can be obtained. Therefore, the glass transition temperature of the optical glass of the present invention is preferably 500℃or higher, more preferably 530℃or higher, and still more preferably 550℃or higher.
The optical glass of the present invention preferably has a yield point (At) of 800℃or lower. The yield point, like the glass transition temperature, is an index indicating the softening property of glass and also an index indicating a temperature close to the press molding temperature. Therefore, even when the optical glass is used for press molding, the glass can be easily press molded at a lower temperature by using the glass having a yield point of 800 ℃. Therefore, the yield point of the optical glass of the present invention is preferably at an upper limit of 800 ℃, more preferably at an upper limit of 750 ℃, and even more preferably at an upper limit of 700 ℃.
The yield point of the optical glass of the present invention is not particularly limited, but is preferably 500℃as a lower limit, more preferably 550℃as a lower limit, and even more preferably 600℃as a lower limit.
The optical glass of the present invention preferably has a small specific gravity. More specifically, the specific gravity of the optical glass of the present invention is 5.00 or less. Accordingly, since the mass of the optical element and the optical instrument using the optical element can be reduced, the reduction in weight of the optical instrument can be facilitated. Accordingly, the specific gravity of the optical glass of the present invention is preferably 5.00 as an upper limit, more preferably 4.70 as an upper limit, and even more preferably 4.50 as an upper limit. The specific gravity of the optical glass of the present invention is generally 3.00 or more, more specifically 3.30 or more, and still more specifically 3.50 or more.
The specific gravity of the optical glass of the present invention was measured based on "method for measuring specific gravity of optical glass" by JOGIS05-1975, japan optical Nitro Industrial Condition Standard.
The optical glass of the present invention preferably has a small average linear expansion coefficient (α). In particular, the average linear expansion coefficient of the optical glass of the present invention is preferably 100X 10 -7 K -1 As an upper limit, it is more preferable to use 90X 10 -7 K -1 As an upper limit, it is more desirable to use 80X 10 -7 K -1 Is the upper limit. Accordingly, when the optical glass is press-molded using the molding die, the total amount of expansion and contraction due to the temperature change of the glass can be reduced. Therefore, the optical glass is hardly broken during press moldingTo improve productivity of the optical element.
Preform and optical element
The optical glass produced can be used to produce a glass molded article by a polishing process, a reheat press molding process, a precision press molding process, or other press molding process. That is, a glass molded article can be produced by mechanically working such as grinding and polishing an optical glass, or by producing a preform for press molding from an optical glass, and then subjecting the preform to reheat press molding and then polishing, or by producing a glass molded article by precision press molding a preform produced by polishing and a preform molded by well-known float molding or the like. The method for producing the glass molded product is not limited to these methods.
Thus, the optical glass of the present invention is useful for various optical elements and optical designs. Among them, it is preferable to form a preform from the optical glass of the present invention, and to use the preform for reheat press molding, precision press molding, and the like to manufacture optical elements such as lenses and prisms. Accordingly, since a preform having a large diameter can be formed, not only can the optical element be enlarged, but also imaging characteristics and projection characteristics with high definition and high precision can be realized when the preform is used in an optical device such as a camera or a projector.
[ example ]
Table 1 to Table 26 show the compositions of examples (No. A1 to No. A73, no. B1 to No. B78, no. C1 to No. C38, no. D1 to No. D6) and comparative examples (No. X) according to the present invention, and the refractive indices (n) d ) Abbe number (v) d ) Glass transition temperature (Tg), yield point (At), liquidus temperature, spectral transmittance, wavelength (lambda) showing 5%, 70%, 80% 5 、λ 70 、λ 80 ) Results of specific gravity and average linear expansion coefficient (α). The examples (No. a1 to No. a73 and No. d1 to No. d 6) mainly show examples of the first optical glass. Examples (No. B1 to No. B78, no. D1 to No. D6) are mainly An example of the second optical glass is shown. Examples (No. c1 to No. c 38) mainly show examples of the third optical glass.
The following embodiments are provided for purposes of illustration and are not limited to these embodiments.
The glasses of examples and comparative examples of the present invention were each produced by selecting high purity raw materials used for general optical glasses such as oxides, hydroxides, carbonates, nitrates, fluorides, hydroxides, metaphosphoric acid compounds, etc., which are raw materials of the respective components, weighing and uniformly mixing the raw materials in the composition ratios of the respective examples shown in the table, 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 2 to 5 hours according to the melting difficulty of the raw materials, stirring the raw materials uniformly, and then pouring the raw materials into a mold to slowly cool the raw materials.
Here, refractive indices (n d ) Abbe number (v) d ) The measurement was performed in accordance with JOGIS01-2003, a Japanese optical nitroprusside Industrial Association standard. Here, refractive index (n d ) Abbe number (v) d ) The glass obtained by slowly cooling at a cooling rate of-25 ℃/hr was measured.
Glass transition temperatures (Tg) and yield points (At) of the glasses of examples and comparative examples were measured using a horizontal dilatometer. Here, the sample used for measurement had a diameter of 4.8mm, a length of 50 to 55mm, and a heating rate of 4℃per minute.
The transmittance of the glasses of examples and comparative examples was measured in accordance with JOGIS02, a Japanese optical nitroprusside Industrial Association standard. In the present invention, the degree and the degree of staining of the glass were determined by measuring the transmittance of the glass. Specifically, for a relatively parallel polished article having a thickness of 10.+ -. 0.1mm, the spectral transmittance of 200 to 800nm was measured according to JIS Z8722 to obtain lambda 5 (wavelength at 5% transmittance), lambda 70 (wavelength at 70% transmittance) and lambda 80 (wavelength at 80% transmittance).
The liquid phase temperatures of the glasses of examples and comparative examples were determined by adding 30cc of a glass sample in a broken glass form to a platinum crucible having a capacity of 50ml, melting the glass sample at 1250℃completely, cooling the glass sample to any one of temperatures set at 10℃for 1 hour at 1200℃to 800℃and then taking the glass sample out of the furnace, and immediately observing the presence or absence of crystals on the surface and in the interior of the glass after cooling the glass sample to obtain the minimum temperature at which no crystals were confirmed.
The specific gravity of the glasses of examples and comparative examples was measured according to the Japanese optical nitroprusside Industrial Association Standard JOGIS05-1975 "method for measuring specific gravity of optical glasses".
The average linear expansion coefficients (α) of the glasses of examples and comparative examples were obtained by the method for measuring thermal expansion of optical glass according to JOGIS08-2003, a Japanese optical nitroindustry Condition standard, and were determined at-30 to +70 ℃.
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
TABLE 5
TABLE 6
TABLE 7
TABLE 8
TABLE 9
Table 10
TABLE 11
Table 12
TABLE 13
TABLE 14
TABLE 15
Table 16
TABLE 17
TABLE 18
TABLE 19
Table 20
Table 21
Table 22
Table 23
Table 24
Table 25
Table 26
As shown in the table, the optical glass according to the examples of the present invention was excellent in the optical characteristics due to the sum of the moles (Nb 2 O 5 +WO 3 ) Less than 10.0%, and thus can be manufactured more inexpensively. On the other hand, the glass of comparative example (No. X), due to the sum of the moles (Nb) 2 O 5 +WO 3 ) 11.53%, so the material cost is high.
The optical glass of the embodiment of the present invention has refractive index (n d ) Are all above 1.70, i.e. within the required range. In particular, the optical glasses of examples (No. A1 to No. A73, no. D1 to No. D6) have refractive indices (n d ) Are each 1.75 or more, more specifically 1.78 or more. In addition, the optical glasses of examples (No. B1 to No. B78) have refractive indices (n d ) All are above 1.74. In addition, the optical glasses of examples (No. C1 to No. C38) have refractive indices (n d ) All are above 1.80.
On the other hand, the optical glass of the embodiment of the present invention has refractive index (n d ) Are all below 2.10. In particular, the optical glasses of examples (No. A1 to No. A73, no. D1 to No. D6) have refractive indices (n d ) Are all below 2.00. The optical glasses of examples (No. B1 to No. B78, no. D1 to No. D6) have refractive indices (n d ) Are all below 1.90. In addition, the optical glasses of examples (No. C1 to No. C38) have refractive indices (n d ) Are all below 2.00.
The optical glass of the embodiment of the present invention has Abbe number (. Nu. d ) Are all below 50, i.e. are as requiredWithin a range of (2). In particular, the optical glasses of examples (No. A1 to No. A73, no. D1 to No. D6) have Abbe numbers (. Nu. d ) Are each 48 or less, more specifically 45 or less. In addition, the optical glasses of examples (No. C1 to No. C38) have Abbe numbers (. Nu) d ) Are all 41 or less.
On the other hand, the optical glass of the embodiment of the present invention has Abbe number (. Nu. d ) Are above 25, i.e. within the required range. In particular, the optical glasses of examples (No. A1 to No. A73, no. D1 to No. D6) have Abbe numbers (. Nu. d ) Are all above 26. In addition, the optical glasses of examples (No. B1 to No. B78, no. D1 to No. D6) have Abbe numbers (. Nu. d ) Are all above 30, more specifically above 32. In addition, the optical glasses of examples (No. C1 to No. C38) have Abbe numbers (. Nu) d ) Are all above 26.
In addition, the optical glass of the present invention forms stable optical glass, and is less likely to undergo devitrification when the glass is manufactured. This can also be estimated from the fact that the liquid phase temperature of the optical glass of the present invention is 1250℃or lower, more specifically 1210℃or lower.
In addition, the optical glass of the embodiment of the invention, lambda 80 (wavelength at 80% transmittance) is 550nm or less, more specifically 490nm or less.
In addition, the optical glass of the embodiment of the invention, lambda 70 (wavelength at 70% transmittance) is 500nm or less, more specifically 490nm or less. In particular, the optical glasses, lambda, of examples (No. C1 to No. C38) 70 All below 450 nm.
In addition, the optical glass of the embodiment of the invention, lambda 5 (wavelength at 5% transmittance) is 400nm or less, more specifically 380nm or less, i.e., within the desired range. In addition, the optical glasses, lambda, of examples (No. C1 to No. C38) 5 Are all below 370 nm.
Thus, it was found that the optical glass according to the embodiment of the present invention had refractive index (n d ) Abbe number (v) d ) All are in the required range, and have higher transmittance to the short wavelength of visible light and higher devitrification resistance.
In addition, the optical glass of the embodiment of the present invention has a glass transition temperature (Tg) of 700 ℃ or less, more specifically 620 ℃ or less.
In addition, the optical glass of the embodiment of the present invention has a yield point (At) of 800 ℃ or less, more specifically 670 ℃ or less.
From the above, it is also assumed that the glass transition temperature and yield point of the optical glass according to the embodiment of the present invention are low.
The specific gravity of the optical glass according to the embodiment of the present invention is 5.00 or less, more specifically 4.50 or less. In particular, the optical glasses of examples (No. B1 to No. B78, no. D1 to No. D6) of the present invention each have a specific gravity of 4.50 or less.
In addition, the optical glass of the example has an average linear expansion coefficient (α) of 100×10 -7 K -1 Hereinafter, more specifically, the ratio is 80X 10 -7 K -1 The following is given.
Further, using the optical glass of the embodiment of the present invention, a glass block was formed, and the glass block was ground and polished to be processed into the shape of a lens and a preform. As a result, various lens and preform shapes can be stably manufactured.
While the present invention has been specifically described above for the purpose of illustration, the present embodiment is always for the purpose of illustration only, and it should be understood that various changes may be made by those skilled in the art without departing from the spirit and scope of the invention.
Claims (12)
1. An optical glass characterized in that it comprises, in mol%,
contains B 2 O 3 The content of La is 10.0-55.0% 2 O 3 The content is 5.0% to 30.0%,
ZnO component 24.06-45.0%, siO 2 The content is more than 5.0% and less than 25.0%,
sum of moles (Nb) 2 O 5 +WO 3 ) Less than 5.0 percent,
and has a refractive index (n) d ) And an Abbe number (v) of 25 to 50 inclusive d )。
2. An optical glass characterized in that it comprises, in mol%,
containing TiO 2 The component is 0 to less than 40.0 percent,
ZrO 2 0 to 15.0 percent of components,
Y 2 O 3 0 to 25.0 percent of component,
BaO component 0-25.0%.
3. The optical glass according to claim 1, wherein the sum of moles Ta 2 O 5 +Nb 2 O 5 +WO 3 +Gd 2 O 3 +Yb 2 O 3 Less than 5.0%.
4. The optical glass according to claim 1, wherein the total amount of at least one of the CaO component and the BaO component is greater than 0% and 30.0% or less, calculated as mol%.
5. An optical glass according to claim 1, wherein the glass is used for the optical glass in mole%,
Nb 2 O 5 The components are 0 to less than 5.0 percent,
WO 3 the components are 0 to less than 5.0 percent,
Gd 2 O 3 the component is 0 to less than 4.0 percent,
Yb 2 O 3 the components are 0 to less than 4.0 percent,
Ta 2 O 5 the components are 0 to less than 5.0 percent,
MgO component is 0-10.0%,
the CaO component is 0 to 10.0 percent,
the SrO component is 0 to 10.0 percent,
Li 2 the O component is 0 to 10.0 percent,
Na 2 the O component is 0 to 10.0 percent,
K 2 the O component is 0 to 10.0 percent,
P 2 O 5 the components are 0 to 10.0 percent,
GeO 2 the components are 0 to 10.0 percent,
Al 2 O 3 the components are 0 to 15.0 percent,
Ga 2 O 3 the components are 0 to 15.0 percent,
Bi 2 O 3 the components are 0 to 15.0 percent,
TeO 2 the components are 0 to 15.0 percent,
SnO 2 the components are 0 to 3.0 percent,
Sb 2 O 3 the components are 0 to 1.0 percent,
the content of F in the fluoride substituted with part or all of the oxide of one or more of the above metal elements is 0 to 15.0 mol%.
6. The optical glass according to claim 1, wherein the molar ratio SiO 2 /B 2 O 3 Is 0.13 to 1.70 inclusive.
7. The optical glass according to claim 1, wherein the molar ratio ZnO/(La) 2 O 3 +Y 2 O 3 ) Is 0.35 to 4.00.
8. The optical glass according to claim 1, wherein,
Ln 2 O 3 the sum of the molar amounts of the components is 5.0% to 40.0%, wherein Ln is 1 or more selected from the group consisting of La, gd, Y, yb, lu,
The sum of the moles of RO components is 25.0% or less, wherein R is 1 or more selected from the group consisting of Mg, ca, sr, ba,
Rn 2 the sum of the moles of the O components is 10.0% or less, wherein Rn is 1 or more selected from the group consisting of Li, na and K.
9. An optical glass according to claim 1, wherein the molar ratio (ro+zno)/Ln 2 O 3 More than 0.30, wherein R is 1 or more selected from the group consisting of Mg, ca, sr, ba, and Ln is 1 or more selected from the group consisting of La, gd, Y, yb, lu.
10. A preform constituted by the optical glass according to any one of claims 1 to 9.
11. An optical element composed of the optical glass according to any one of claims 1 to 9.
12. An optical instrument provided with the optical element according to claim 11 or 12.
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| JP2015-218906 | 2015-11-06 | ||
| JP2015-218905 | 2015-11-06 | ||
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| JP2015218904 | 2015-11-06 | ||
| JP2015218906 | 2015-11-06 | ||
| JP2016137864 | 2016-07-12 | ||
| JP2016137865A JP6808385B2 (en) | 2015-11-06 | 2016-07-12 | Optical glass, preform materials and optical elements |
| JP2016-137865 | 2016-07-12 | ||
| JP2016-137864 | 2016-07-12 | ||
| JP2016-210892 | 2016-10-27 | ||
| JP2016210891A JP6903373B2 (en) | 2015-11-06 | 2016-10-27 | Optical glass, preform materials and optical elements |
| JP2016-210891 | 2016-10-27 | ||
| JP2016210892A JP6866012B2 (en) | 2015-11-06 | 2016-10-27 | Optical glass, preform materials and optical elements |
| CN201610965483.8A CN106927675A (en) | 2015-11-06 | 2016-11-04 | A kind of optical glass, prefabricated component and optical element |
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| CN110316960B (en) * | 2019-07-22 | 2022-02-11 | 成都光明光电股份有限公司 | Optical glass, glass preform, optical element and optical instrument |
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| JP3912774B2 (en) * | 2002-03-18 | 2007-05-09 | Ｈｏｙａ株式会社 | Optical glass for precision press molding, preform for precision press molding and manufacturing method thereof |
| DE10227494C1 (en) * | 2002-06-19 | 2003-12-04 | Schott Glas | Lead-free optical glass with specified refractive index and Abbe number, for optics, laser technology and communications, has specified composition |
| EP1433757B1 (en) * | 2002-12-27 | 2017-02-01 | Hoya Corporation | Optical glass, press-molding glass gob and optical element |
| JP4361004B2 (en) * | 2004-11-15 | 2009-11-11 | Ｈｏｙａ株式会社 | Optical glass, precision press-molding preform and manufacturing method thereof, and optical element and manufacturing method thereof |
| JP4322217B2 (en) * | 2005-02-21 | 2009-08-26 | Ｈｏｙａ株式会社 | Optical glass, glass gob for press molding, optical component, method for manufacturing glass molded body, and method for manufacturing optical component |
| JP4756554B2 (en) * | 2006-03-23 | 2011-08-24 | Ｈｏｙａ株式会社 | Optical glass, precision press-molding preform and manufacturing method thereof, and optical element and manufacturing method thereof |
| JP2008233547A (en) * | 2007-03-20 | 2008-10-02 | Hoya Corp | Lens glass material for on-vehicle camera and lens for on-vehicle camera |
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| TW201731785A (en) | 2017-09-16 |
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