CN117486484A - Optical glass, prefabricated member and optical element - Google Patents
Optical glass, prefabricated member and optical element Download PDFInfo
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- CN117486484A CN117486484A CN202311460255.1A CN202311460255A CN117486484A CN 117486484 A CN117486484 A CN 117486484A CN 202311460255 A CN202311460255 A CN 202311460255A CN 117486484 A CN117486484 A CN 117486484A
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- 239000005304 optical glass Substances 0.000 title claims abstract description 92
- 230000003287 optical effect Effects 0.000 title claims description 38
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- 239000011521 glass Substances 0.000 claims description 105
- 230000009477 glass transition Effects 0.000 claims description 27
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 15
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 7
- 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
- 238000005498 polishing Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims 1
- NAXKFVIRJICPAO-LHNWDKRHSA-N [(1R,3S,4R,6R,7R,9S,10S,12R,13S,15S,16R,18S,19S,21S,22S,24S,25S,27S,28R,30R,31R,33S,34S,36R,37R,39R,40S,42R,44R,46S,48S,50R,52S,54S,56S)-46,48,50,52,54,56-hexakis(hydroxymethyl)-2,8,14,20,26,32,38,43,45,47,49,51,53,55-tetradecaoxa-5,11,17,23,29,35,41-heptathiapentadecacyclo[37.3.2.23,7.29,13.215,19.221,25.227,31.233,37.04,6.010,12.016,18.022,24.028,30.034,36.040,42]hexapentacontan-44-yl]methanol Chemical compound OC[C@H]1O[C@H]2O[C@H]3[C@H](CO)O[C@H](O[C@H]4[C@H](CO)O[C@H](O[C@@H]5[C@@H](CO)O[C@H](O[C@H]6[C@H](CO)O[C@H](O[C@H]7[C@H](CO)O[C@@H](O[C@H]8[C@H](CO)O[C@@H](O[C@@H]1[C@@H]1S[C@@H]21)[C@@H]1S[C@H]81)[C@H]1S[C@@H]71)[C@H]1S[C@H]61)[C@H]1S[C@@H]51)[C@H]1S[C@@H]41)[C@H]1S[C@H]31 NAXKFVIRJICPAO-LHNWDKRHSA-N 0.000 abstract 2
- 238000004031 devitrification Methods 0.000 description 41
- 239000002994 raw material Substances 0.000 description 40
- 230000005484 gravity Effects 0.000 description 25
- 238000002834 transmittance Methods 0.000 description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- 238000000465 moulding Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 239000006060 molten glass Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 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 5
- 229960002460 nitroprusside Drugs 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000003384 imaging method 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
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910005690 GdF 3 Inorganic materials 0.000 description 1
- 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
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910008449 SnF 2 Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 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
- 238000000748 compression moulding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229940093920 gynecological arsenic compound Drugs 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000004554 molding of glass Methods 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
- 230000000704 physical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
- C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
- C03C3/155—Silica-free oxide glass compositions containing boron containing rare earths containing zirconium, titanium, tantalum or niobium
-
- 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
- G02B1/002—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials
Abstract
The invention provides an optical glass with a refractive index (n d ) Abbe number (v) d ) Are allIn the required range and has higher stability. The optical glass contains B based on mole of oxide 2 O 3 More than 44.0% of the components and less than 55.0% of Ln 2 O 3 More than 7.0% and less than 11.0% of components, wherein Ln is more than 1 selected from the group consisting of La, gd, Y, yb, siO 2 The content of Li is more than 7.0% and less than 12.5% 2 The O component is more than 7.0% and less than 13.0%, zrO 2 The composition is more than 1.0% and less than 5.0%, ta 2 O 5 The content of the component (A) is less than 1.0%, and the sum of the moles of the oxide basis (ZnO+Li) 2 O) is greater than 25.0% and 40.0% or less, and has a refractive index n of 1.60 to 1.80 d An Abbe number v of 40 to 60 d 。
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 optical glass for manufacturing optical elements, particularly, a glass having a high refractive index (n) of 1.60 to 1.80 (n d ) And a high Abbe number (v) of 40 to 60 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, a glass composition described in patent document 1 is widely known.
Japanese patent document No. 2003-020249
Technical problem to be solved by the invention
In order to reduce the material cost of the optical glass, it is required that the raw material cost of the optical glass is as low as possible. However, the glass described in patent document 1 is difficult to sufficiently satisfy such a requirement.
The glass described in patent document 1 has a problem that the specific gravity of the glass is high and the quality of the optical element is high. That is, when these glasses are used in optical instruments such as cameras and projectors, there is a problem that the quality of the entire optical instrument tends to be large.
However, the glass disclosed in patent document 1 has a high refractive index and low dispersion, but has a high glass transition temperature, and therefore cannot be said to be a glass that is ideal for press molding. In addition, the glass disclosed in patent document 1 is hardly said to have high stability, and may exhibit a phenomenon such as devitrification.
On the other hand, even when the material cost and glass transition temperature of the optical glass are reduced, an optical glass having high stability and less susceptibility to devitrification is still demanded.
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) 3 ) All are within the required range, and the stability is higher.
In addition, the invention also aims to obtain a refractive index (n d ) Abbe number (v) d ) The optical glass has higher stability, lower glass transition temperature and ideal stamping forming.
Disclosure of Invention
The inventors of the present invention have found that B is contained in the composition as a result of repeated intensive experiments and studies to solve the above problems 2 O d Composition and Ln 2 O 3 In glasses of composition, even in the more expensive Ta 2 O 5 With a small content of the components, a glass having a desired high refractive index and low dispersion and having high stability can be obtained, and the present invention has been completed.
Specifically, the present invention provides the following optical glass.
(1) An optical glass characterized by comprising, in mole% based on oxides, B 2 O 3 More than 44.0% of the components and less than 55.0% of Ln 2 O 3 Component 7.0%Wherein Ln is at least 1 selected from the group consisting of La, gd, Y, yb,
SiO 2 the composition is more than 7.0% and less than 12.5%,
Li 2 the O component is more than 7.0% and less than 13.0%,
ZrO 2 the composition is more than 1.0 percent and less than 5.0 percent,
Ta 2 O 5 the content of the component (A) is less than 1.0%, and the sum of the moles of the oxide basis (ZnO+Li) 2 O) is greater than 25.0% and 40.0% or less, and has a refractive index n of 1.60 to 1.80 d An Abbe number v of 40 to 60 d 。
(2) The optical glass according to the above (1), wherein the glass is produced by, in mol% based on the oxide,
La 2 O 3 the components are 0 to 20.0 percent,
Gd 2 O 3 the components are 0 to 10.0 percent,
Y 2 O 3 the components are 0 to 15.0 percent,
Yb 2 O 3 the components are 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,
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 10.0 percent,
ZnO component is 0-25.0%,
TiO 2 the components are 0 to 20.0 percent,
Nb 2 O 5 the components are 0 to 15.0 percent,
WO 3 the components are 0 to 10.0 percent,
P 2 O 5 the components are 0 to 15.0 percent,
GeO 2 the components are 0 to 15.0 percent,
Al 2 O 3 the components are 0 to 15.0％，
Ga 2 O 3 The components are 0 to 15.0 percent,
Bi 2 O 3 the components are 0 to 10.0 percent,
TeO 2 the components are 0 to 15.0 percent,
SnO 2 The components are 0 to 5.0 percent
Sb 2 O 3 The components are 0 to 1.0 percent.
(3) The optical glass according to the above (1), wherein the sum (B) of the moles of the oxide basis 2 O 3 +SiO 2 ) 53.0% or more and less than 65.0%.
(4) The optical glass according to the above (1), wherein Rn calculated on an oxide basis 2 The sum of the moles of the O components is 20.0% or less, wherein Rn is 1 or more selected from the group consisting of Li, na and K,
the sum of the moles of RO components is 10.0% or less, wherein R is 1 or more selected from the group consisting of Mg, ca, sr, ba.
(5) The optical glass according to the above (1), wherein the sum of the moles of the oxide basis (RO+Rn) 2 O) is more than 7.0% and 25.0% or less, wherein Rn is 1 or more selected from the group consisting of Li, na, and K, and R is 1 or more selected from the group consisting of Mg, ca, sr, ba.
(6) The optical glass according to the above (1), wherein the molar ratio ZnO/(ZnO+RO) based on the oxide is 0.50 or more, wherein R is 1 or more selected from the group consisting of Mg, ca, sr, ba.
(7) The optical glass according to the above (1), wherein the sum of the moles of the oxide basis (ZnO+ZrO) 2 ) More than 15.0% and less than 35.0%.
(8) The optical glass according to the above (1), wherein the glass transition temperature Tg is 600℃or lower.
(9) An optical element comprising the optical glass according to any one of the above (1) to (8).
(10) A preform comprising the optical glass according to any one of the above (1) to (8) and used for polishing and/or precision press molding.
(11) An optical element, characterized in that the preform of (10) is precision press-worked.
Effects of the invention
According to the present invention, a refractive index (n d ) Abbe number (v) d ) All are within the required range, and the stability is higher.
Furthermore, according to the present invention, a refractive index (n d ) Abbe number (v) d ) The optical glass has higher stability and lower glass transition temperature and is ideal for stamping forming.
Drawings
FIG. 1 is a graph of refractive index (n) d ) With Abbe number (v) d ) Is a schematic diagram of the relationship of (a).
Detailed Description
The optical glass of the present invention comprises, based on the mole of the oxide, B 2 O 3 Component 2544.0% or more and less than 55.0%, ln 2 O 3 Wherein Ln is at least 1 selected from the group consisting of La, gd, Y, yb,
SiO 2 the composition is more than 7.0% and less than 12.5%,
Li 2 the O component is more than 7.0% and less than 13.0%,
ZrO 2 the composition is more than 1.0 percent and less than 5.0 percent,
Ta 2 O 5 the content of the component (A) is less than 1.0%, and the sum of the moles of the oxide basis (ZnO+Li) 2 O) is greater than 25.0% and 40.0% or less, and has a refractive index n of 1.60 to 1.80 d An Abbe number v of 40 to 60 d 。
According to the invention in the presence of B 2 O 3 Composition and Ln 2 O 3 In glasses of composition, even in the more expensive Ta 2 O 5 With a small content of the components, a glass having a desired high refractive index and low dispersion and having high stability can be obtained. Therefore, the refractive index (n) d ) Abbe number (v) d ) All are within the required range, and the stability is higher.
The embodiments of the optical glass of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and may 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 are as follows. In the present specification, unless otherwise specified, the content of each component is expressed in mole% based on the oxide. The composition of the "oxide standard" herein means a composition of each component contained in glass, assuming that an oxide, a double salt, a fluoride, or the like used as a glass raw material is completely decomposed and converted to an oxide at the time of melting, with the total mole number of the oxide to be formed being 100 mole%.
< essential component, optional component >
B 2 O 3 The component (a) is an essential component 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 it contain B 2 O 3 The component of 44.0% or more can improve devitrification resistance of the glass, increase Abbe number, and reduce specific gravity. Thus B 2 O 3 The content of the component (A) is preferably at a lower limit of 25%, more preferably at a lower limit of 30%, even more preferably at a lower limit of 40%, even more preferably at a lower limit of 44%, and even more preferably at a lower limit of 47.0%.
On the other hand, by making B 2 O 3 The content of the component is 70.0% or less, and a decrease in refractive index and a decrease in chemical durability can be suppressed. Thus B 2 O 3 The content of the component (A) is preferably less than 70.0%, more preferably less than 65%, still more preferably less than 60%, and still more preferably less than 55%.
B 2 O 3 As the component (A), H can be used as a raw material 2 BO 3 、Na 2 B 4 O 7 、Na 2 B 4 O 7 ·10H 2 O、BPO 4 Etc.
Ln 2 O 3 The sum (molar sum) of the contents of the components (wherein Ln is 1 or more selected from the group consisting of La, gd, Y, yb) is 3.0% to 20.0%.
In particular, when the sum of the molar amounts is 3.0% or more, the refractive index and abbe number of the glass can be increased, and thus a high refractive index low dispersion glass can be obtained relatively easily. Thus Ln 2 O 3 The sum of the molar amounts of the components is preferably 3.0% as a lower limit, more preferably 5.0% as a lower limit, and still more preferably 7.0% as a lower limit.
On the other hand, when the sum of the molar amounts is 20.0% or less, the liquidus temperature of the glass can be reduced, and the devitrification resistance can be improved. In addition, the material cost of the glass can be suppressed accordingly. Thus Ln 2 O 3 The molar sum of the contents of the components is preferably 20.0% or less, more preferably less than 17.0%, still more preferably less than 14.0%, still more preferably less than 11.0%, still more preferably less than 10.0%.
Ta 2 O 5 When the content exceeds 0%, the refractive index and the devitrification resistance can be improved, and the viscosity of the molten glass can be increased.
On the other hand, by making Ta 2 O 5 The content of the components is less than 5.0%, and the rare mineral resource Ta is reduced 2 O 5 The amount of the components used can be reduced to thereby reduce the glassIs not limited by the material cost of (a). In addition, the specific gravity can be reduced accordingly. 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%, and even more preferably less than 0.1%.
Ta 2 O 5 As the component, ta may be used as a raw material 2 O 5 Etc.
La 2 O 3 The component (a) is any component that can increase the refractive index of glass and reduce dispersion (increase abbe number). In addition, by containing La 2 O 3 The component (A) can reduce the content of other rare earth elements for increasing specific gravity, so that glass with smaller specific gravity can be obtained more easily. Therefore La 2 O 3 The content of the component (A) is preferably more than 0%, more preferably 1.0% as a lower limit, still more preferably 4.0% as a lower limit, and still more preferably 6.0% as a lower limit.
On the other hand, by making La 2 O 3 The content of the component is 20.0% or less, whereby the glass stability can be improved to reduce devitrification and the Abbe number can be suppressed from rising. Therefore La 2 O 3 The content of the component (A) is preferably 20.0% or less, more preferably less than 17.0%, still more preferably less than 14.0%, still more preferably less than 11.0%, still more preferably less than 9.0%.
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.
SiO 2 When the content exceeds 0%, the viscosity of the molten glass can be increased, the staining of the glass can be reduced, and the devitrification resistance can be improved. 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 4.0%, and still more preferably more than 7.0%.
On the other hand, by making SiO 2 The content of the component is below 20.0%, and the decrease of refractive index can be suppressedAnd an increase in glass transition temperature, and the specific gravity can be reduced. Thus, siO 2 The content of the component (A) is preferably 20.0% as an upper limit, more preferably 15.0% as an upper limit, and still more preferably 12.5% as an upper limit.
SiO 2 SiO can be used as a raw material 2 、K 2 SiF 6 、Na 2 SiF 6 Etc.
Li 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%. Thus Li 2 The content of the O component is preferably more than 0%, more preferably more than 2.0%, still more preferably more than 3.0%, still more preferably more than 5.0%, still more preferably more than 6.0%, still more preferably more than 7.0%, still more preferably more than 9.0%.
On the other hand, by making Li 2 The content of the O component is 20.0% or less, which can reduce the decrease in refractive index and devitrification and can improve chemical durability. In addition, the viscosity of the molten glass can be increased, and thus occurrence of glass streaks can be reduced. Thus Li 2 The content of the O component is preferably 20.0% or less, more preferably less than 15.0%, and still more preferably less than 13.0%.
Li 2 As the raw material for the O component, li can be used 2 CO 3 、LiNO 3 LiF, etc.
The ZnO component is any component that can lower the glass transition temperature, reduce the specific gravity, and improve the chemical durability when the content exceeds 0%. Accordingly, the content of the ZnO component is preferably more than 0%, more preferably more than 1.0%, even more preferably more than 5.0%, even more preferably more than 9.0%, even more preferably more than 12.0%, even more preferably more than 14.0%, and even more preferably 15.7% or more.
On the other hand, by setting the content of the ZnO component to 25.0% or less, the decrease in refractive index and devitrification can be reduced. In addition, the viscosity of the molten glass can be increased, and thus occurrence of glass streaks can be reduced. Accordingly, the content of the ZnO component is preferably at an upper limit of 25.0%, more preferably at an upper limit of 22.0%, even more preferably at an upper limit of 20.0%, and even more preferably at an upper limit of 17.0%.
As the ZnO component, znO and ZnF can be used as raw materials 2 Etc.
ZrO 2 When the content exceeds 0%, the glass can have a high refractive index and a low dispersion (high abbe number), 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%, still more preferably at least 2.5%, still more preferably at least 3.7%, still more preferably at least 4.2%.
On the other hand, by making ZrO 2 The content of the component (A) is 10.0% or less, and the decrease in devitrification resistance due to the excessive content can be suppressed. Thus, zrO 2 The content of the component (A) is preferably at an upper limit of 10.0%, more preferably at an upper limit of 8.0%, even more preferably at an upper limit of 6.0%, and still more preferably at an upper limit of 5.0%.
ZrO 2 As the component (A) as a raw material, zrO may be used 2 、ZrF 4 Etc.
Gd 2 O 3 When the content exceeds 0%, the refractive index and the abbe number can be increased, and the devitrification resistance can be improved.
On the other hand, by making Gd 2 O 3 The content of the component is 10.0% or less, so that devitrification resistance can be improved and increase in specific gravity can be suppressed. In particular by reducing Gd 2 O 3 The content of the components can control the material cost of the glass. Thus Gd 2 O 3 The content of the component (A) is preferably 10.0% or less, more preferably less than 5.0%, still more preferably less than 3%, and still more preferably less than 1.0%.
Gd 2 O 3 Gd can be used as the raw material 2 O 3 、GdF 3 Etc.
Y 2 O 3 When the content exceeds 0%, the refractive index and Abbe number can be increased, the specific gravity can be reduced, and the devitrification resistance can be improved. Thus Y 2 O 3 The content of the component (A) is preferably more than 0%, more preferably more than 0.5%, still more preferably more than 1.0%.
On the other hand, by making Y 2 O 3 The content of the component is 15.0% or less, and devitrification due to excessive content can be reduced. Thus Y 2 O 3 The content of the component (A) is preferably 15.0% or less, more preferably less than 10.0%, still more preferably less than 6.0%, and still more preferably less than 3.0%.
Y 2 O 3 As the component (A), Y can be used as a raw material 2 O 3 、YF 3 Etc.
Yb 2 O 3 When the content exceeds 0%, the refractive index and the abbe number can be increased, and the devitrification resistance can be improved.
On the other hand, by making Yb 2 O 3 The content of the component is 10.0% or less, devitrification due to excessive content can be reduced, increase in specific gravity can be suppressed, and the material cost of the glass can be controlled. Thus Yb 2 O 3 The content of the component (A) is preferably 10.0% or less, more preferably less than 5.0%, still more preferably less than 3.0%, and still more preferably less than 1.0%.
Yb 2 O 3 Yb can be used as a raw material for the component 2 O 3 Etc.
Na 2 O component and K 2 When the content of at least one of the O components exceeds 0%, the glass raw material can be improved in melting property, devitrification resistance can be improved, and the glass transition temperature can be reduced.
On the other hand, by making Na 2 O component and K 2 The content of each O component is 10.0% or less, which makes it difficult to lower the refractive index and reduces the amount of the O component caused by excessive contentDevitrification. Thus, 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%, still more preferably less than 3.0%, and still more preferably less than 1.0%.
Na 2 O component and K 2 As the O component, na may be used as a raw material 2 CO 3 、NaNO 3 、NaF、Na 2 SiF 3 、K 2 CO 3 、KNO 3 、KF、KHF 2 、K 2 SiF 6 Etc.
The MgO component, the CaO component, and the SrO component are any components that can improve the meltability of the glass raw material and the devitrification resistance of the glass when the content of at least one of them exceeds 0%. In particular, the MgO component and the CaO component may be components that reduce specific gravity by being contained.
On the other hand, by setting the respective contents of the MgO component, srO component, and CaO component to 10.0% or less, it is possible to reduce the decrease in refractive index and devitrification caused by excessively containing these components. Accordingly, the content of each of the MgO component, srO component, and CaO component is preferably 10.0% or less, more preferably less than 8.0%, still more preferably 4.5% or less, and still more preferably less than 3.0%.
As the MgO component, caO component and SrO component, maCO can be used as a raw material 3 、MaF 2 、CaCO 3 、CaF 2 、Sr(NO 3 ) 2 、SrF 2 Etc.
The BaO component is any component that can increase the glass refractive index and control the material cost, and can increase the meltability and devitrification resistance of the glass raw material when the content exceeds 0%.
On the other hand, by setting the content of the BaO component to 10.0% or less, devitrification and an increase in specific gravity due to an excessive content can be suppressed. Therefore, the content of BaO component is preferably 10.0% or less, more preferably less than 5.0%, and still more preferably less than 3.0%.
BaO component, baCO can be used as raw material 3 、Ba(NO 3 ) 2 、BaF 2 Etc.
TiO 2 The component (A) is any component which can increase the refractive index, decrease the specific gravity and improve the stability when the content exceeds 0%. Thus, tiO 2 The content of the component (A) is preferably more than 0%, more preferably more than 0.02%.
On the other hand, by making TiO 2 The content of the component is 20.0% or less, whereby lowering of Abbe number can be suppressed, visible light transmittance can be improved, and devitrification due to excessive content can be suppressed. Thus TiO 2 The content of the component (A) is preferably 20.0% or less, more preferably less than 10.0%, and still more preferably less than 5.0%.
TiO 2 TiO can be used as a raw material for the component 2 Etc.
Nb 2 O 5 When the content exceeds 0%, the refractive index and the devitrification resistance of the glass can be improved.
On the other hand, by making Nb 2 O 5 The content of the component is 15.0% or less, and a decrease in Abbe number, a decrease in devitrification resistance, and a decrease in visible light transmittance due to excessive content can be suppressed. In addition, the specific gravity of the glass can be reduced and the material cost can be controlled accordingly. Thus, nb 2 O 5 The content of the component (A) 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%.
Nb 2 O 5 The component (A) may be Nb 2 O 5 Etc.
WO 3 When the content exceeds 0%, the refractive index can be increased, the glass transition temperature can be lowered, and the devitrification resistance can be improved.
On the other hand, by making WO 3 The content of the component is 10.0% or less, the reduction of Abbe number of the glass can be suppressed, the transmittance of visible light is hardly reduced, and the material cost can be controlled. Thus, WO 3 Composition of the componentsThe content of (2) is preferably 10.0% or less, more preferably less than 5.0%, still more preferably less than 3.0%, and still more preferably less than 1.0%.
WO 3 As the component (A), WO can be used as a raw material 3 Etc.
P 2 O 5 The component (A) is any component which can improve the devitrification resistance when the content exceeds 0%.
On the other hand, by making P 2 O 5 The content of the component (A) is 15.0% 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 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%.
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 cost of the raw material is high, and if the amount is large, the cost of the material increases, so that the effect of reducing the cost due to the reduction of the Ta2O5 component or the like can be reduced. Thus, geO 2 The content of the component (A) 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 1.0%.
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 The component (A) is any component which can improve chemical durability and devitrification resistance when the content exceeds 0%.
On the other hand, by making Al 2 O 3 Composition and Ga 2 O 3 The content of each component is below 15.0%To reduce devitrification caused by excessive content. Thus Al is provided with 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%, still more preferably less than 5.0%, and still 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 is 10.0% or less, whereby the reduction of the Abbe number and the reduction of the devitrification resistance of the glass can be suppressed, and the dyeing of the glass can be reduced and the visible light transmittance can be improved. Bi is therefore 2 O 3 The content of the component (A) is preferably 10.0% or less, more preferably less than 5.0%, still more preferably less than 3.0%, and still 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, by making TeO 2 The content of the components is below 15.0%, which can reduce the dyeing of the glass and improve the visible light transmittance. In addition, 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%, still more preferably less than 5.0%, and still more preferably less than 1.0%.
TeO 2 The components can be used as raw materialsBy TeO 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 5.0% 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 5.0% as an upper limit, more preferably 3.0% as an upper limit, still more preferably 1.0% as an upper limit, and 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% as an upper limit, more preferably 0.5% as an upper limit, and still more preferably 0.3% as an upper limit.
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.
The component for clearing and defoaming glass is 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 a combination thereof.
B 2 O 3 Composition and SiO 2 The sum of the contents (molar sum) of the components is preferably 30.0% to 75.0%.
In particular, by making the sum at 30.0% or more, B can be suppressed 2 O 3 Composition and SiO 2 The lack of components causes a decrease in devitrification resistance. Thus, the sum of moles (B) 2 O 3 +SiO 2 ) The lower limit is preferably 30.0%, more preferably 40.0%, even more preferably 50.0%, even more preferably 53.0%, and even more preferably 56.0%.
On the other hand, by making the sum at 75.0% or less, a decrease in refractive index due to excessive content of these components can be suppressed, and thus a desired high refractive index can be easily obtained. Thus, the sum of moles (B) 2 O 3 +SiO 2 ) More preferably, the content is 75.0% or less, still more preferably, less than 70.0%, still more preferably, less than 65.0%, still more preferably, less than 62.0%.
Rn 2 The sum (molar sum) of the contents of the O component (wherein Rn is at least one selected from the group consisting of Li, na, and K) is preferably 20.0% or less.
Accordingly, the decrease in refractive index of the glass can be suppressed, and devitrification can be reduced. Therefore, the sum of the molar amounts of the Rn2O components is preferably 20.0% or less, more preferably less than 18.0%, still more preferably less than 15.0%, and still more preferably less than 13.0%.
On the other hand, by making the sum larger than 0%, the meltability of the glass raw material and the stability of the glass can be improved. Thus Rn 2 The total content of the O component is preferably more than 0%, more preferably more than 2.0%, still more preferably more than 3.0%, still more preferably more than 5.0%, still more preferably more than 7.0%, still more preferably more than 9.0.
The sum (molar sum) of the contents of the RO component (wherein R is one or more selected from the group consisting of Mg, ca, sr, ba) is preferably 10.0% or less. Accordingly, devitrification caused by excessive content of RO component can be reduced, and a decrease in refractive index can be suppressed. Accordingly, the total content of RO components is preferably 10.0%, more preferably 7.0%, even more preferably 4.5% or less, and still more preferably less than 3.0%.
RO component (wherein R is one or more selected from the group consisting of Mg, ca, sr, ba) and Rn 2 The sum (molar sum) of the contents of the O component (wherein Rn is at least one selected from the group consisting of Li, na, and K) is preferably at least 5.0% and at most 25.0%.
In particular, by setting the sum to 5.0% or more, the stability of the glass can be improved. Thus, the sum of moles (RO+Rn) 2 O) is preferably 5.0% or more, more preferably more than 7.0%, and still more preferably more than 9.0%.
On the other hand, by making the sum equal to or less than 25.0%, a decrease in refractive index can be suppressed. Thus, the sum of moles (RO+Rn) 2 O) is preferably 25.0% or less, more preferably less than 20.0%, even more preferably less than 17.0%, even more preferably less than 16.0%, and even more preferably 12.7% or less.
Relative to B 2 O 3 Composition and SiO 2 Total content of components, RO component (wherein R is one or more selected from the group consisting of Mg, ca, sr, ba) and Rn 2 The total content ratio (molar ratio) of the O component (wherein Rn is at least one selected from the group consisting of Li, na, and K) is preferably at least 0.050 and at most 0.500.
By adjusting the molar ratio, the stability of the glass can be improved and devitrification can be reduced. Thus, the molar ratio (RO+Rn 2 O)/(B 2 O 3 +SiO 2 ) More preferably 0.050 or more, still more preferably more than 0.070, and still more preferably more than 1.000. In addition, the molar ratio (RO+Rn) 2 O)/(B 2 O 3 +SiO 2 ) Preferably, the ratio is 0.500 or less, more preferably less than 0.400, still more preferably less than 0.300, and still more preferably 0.225 or less.
The content ratio (molar ratio) of the ZnO component to the sum of the contents of the ZnO component and the RO component (wherein R is one or more selected from the group consisting of Mg, ca, sr, ba) is preferably 0.50 or more.
Accordingly, not only the stability of the glass can be improved, but also the glass transition temperature can be reduced. Therefore, the molar ratio ZnO/(zno+ro) is preferably 0.50 as a lower limit, more preferably 0.60 as a lower limit, still more preferably 0.70 as a lower limit, and still more preferably 0.80 as a lower limit.
On the other hand, the upper limit of the ratio may be 1.00.
ZnO component and ZrO 2 The sum of the contents (molar sum) of the components is preferably 10.0% to 35.0%.
In particular, by making the sum at 10.0% or more, the stability of the glass can be improved, and the refractive index can be improved. Thus, the sum of the moles (ZnO+ZrO) 2 ) More preferably, it is 10.0% or more, still more preferably, it is more than 15.0%, still more preferably, it is more than 18.0%, still more preferably, it is more than 20.0%, still more preferably, it is 21.0% or more.
On the other hand, by making the sum at 35.0% or less, devitrification due to excessive content can be suppressed. Thus, the sum of the moles (ZnO+ZrO) 2 ) Preferably, the content is not more than 35.0%, more preferably not more than 30.0%, still more preferably not more than 25.0%, and still more preferably not more than 22.0%.
ZnO component and Li 2 The sum of the contents (molar sum) of the O components is preferably 10.0% to 40.0%.
In particular, by making the sum at 10.0% or more, the glass transition temperature can be made lower, and the increase in the glass transition temperature can be made
Stability of the glass. Thus, the sum of moles (ZnO+Li) 2 O), preferably 10.0% or more, more preferably 12.0%, even more preferably 14.0%, even more preferably 17.0%, even more preferably 20.0%, even more preferably 23.0%, even more preferably 25.0%.
On the other hand, by making the sum equal to or less than 40.0%, the decrease in refractive index and devitrification due to the excessive content can be suppressed. Thus, the sum of moles (ZnO+Li) 2 O) is preferably 40.0% or less, more preferably less than 35.0%, and still more preferably less than 30.0%.
TiO 2 Component, nb 2 O 5 Ingredients and WO 3 The sum of the contents (molar sum) of the components is preferably 20.0% or less. Accordingly, lowering of the Abbe number of the glass can be suppressed to achieve low dispersion, and dyeing and devitrification caused by excessive content of these components can be reduced. Thus, the sum of moles (TiO 2 +Nb 2 O 5 +WO 3 ) More preferably, the content is 20.0% or less, still more preferably less than 10.0%, still more preferably less than 5.0%, still more preferably less than 3.0%.
< 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.
Other components may be added as necessary within a range not to deteriorate the glass characteristics of the present invention. However, since each transition metal component such as V, cr, mn, fe, co, ni, cu, ag and Mo has a characteristic that the 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, it is preferable that the transition metal component is not substantially contained in the optical glass using a wavelength in the visible region, in particular.
In addition, lead compounds such As PbO and As 2 O 3 Since arsenic compounds are components with a high environmental burden, they are not substantially contained, that is, are 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, it is preferable that these components are not substantially contained in the case where the influence on the environment is emphasized.
[ method of production ]
The optical glass of the present invention is 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, and the mixture thus produced is put into a platinum crucible, a quartz crucible or an alumina crucible, and then, is put into the platinum crucible, the platinum alloy crucible or the iridium crucible, and is melted in a temperature range of 1100 to 1400 ℃ for 35 hours, and then, is uniformly stirred and defoamed, and then, is finally stirred and removed after the temperature is lowered to 1000 to 1300 ℃, and is poured into a mold, and is slowly cooled, thereby producing the alloy.
< physical Properties >
The optical glass of the present invention has a high refractive index and low dispersion (high abbe number).
In particular, the refractive index (n d ) The lower limit is preferably 1.60, more preferably 1.63, even more preferably 1.65, and even more preferably 1.67. The upper limit of the refractive index is preferably 1.80 or less, more preferably less than 1.75, still more preferably 1.72 or less, still more preferably 1.70 or less, still more preferably 1.695 or less. The Abbe number (v) d ) Preferably, the ratio is set to 40 as a lower limit, more preferably 45 as a lower limit, still more preferably 48 as a lower limit, still more preferably 50 as a lower limit, still more preferably 52 as a lower limit, yet more preferably 60 as an upper limit, still more preferably 58 as an upper limit, and still more preferably 55 as an upper limit.
The optical glass of the present invention has such a refractive index and abbe number, and is therefore useful for optical design, and in particular, not only can achieve high imaging characteristics and the like and miniaturization of an optical system, but also can expand the degree of freedom of optical design.
Here, the optical glass of the present invention has refractive index (n d ) Abbe number (v) d ) Preferably meets (-0.01 v) d +2.13)≦n d ≦(-0.01v d +2.23). The glass with specific composition of the invention is prepared by the following steps ofRefractive index (n) d ) Abbe number (v) d ) Satisfying this relationship, a more stable glass can be obtained.
Therefore, in the optical glass of the present invention, the refractive index (n d ) Abbe number (v) d ) Preferably satisfy n d ≧(-0.01v d +2.13), more preferably satisfying n d ≧(-0.01v d +2.17), more preferably satisfying n d ≧(-0.01v d +2.21).
On the other hand, in the optical glass of the present invention, the refractive index (n d ) Abbe number (v) d ) Preferably satisfy n d ≦(-0.01v d +2.33), more preferably satisfying n d ≦(-0.01v d +2.29), more preferably satisfying n d ≦(-0.01v d +2.25).
The optical glass of the present invention preferably has a glass transition temperature of 600 ℃ or lower. Accordingly, since the glass is softened at a lower temperature, the glass can be press-molded at a lower temperature. In addition, a longer service life of the mold can be achieved by reducing oxidation of the mold for compression molding. Therefore, the glass transition temperature of the optical glass of the present invention is preferably at an upper limit of 600 ℃, more preferably at an upper limit of 580 ℃, and even more preferably at an upper limit of 560 ℃.
The lower limit of the glass transition temperature of the optical glass of the present invention is not particularly limited, but the glass transition temperature of the optical glass of the present invention is preferably 400℃as a lower limit, more preferably 450℃as a lower limit, and even more preferably 500 ℃.
The optical glass of the present invention preferably has a yield point (At) of 700 ℃. The yield point is an index indicating the softening property of glass, like the glass transition temperature, and is also an index indicating a temperature close to the press molding temperature. Therefore, by using glass having a yield point of 700 ℃ or less, press molding can be performed at a lower temperature, and thus press molding can be performed more easily. Therefore, the yield point of the optical glass of the present invention is preferably at an upper limit of 700 ℃, more preferably at an upper limit of 650 ℃, and most preferably at an upper limit of 630 ℃.
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 530℃as a lower limit, and still more preferably 550℃as a lower limit.
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 Is 9×10 as the upper limit -7 K -1 At an upper limit, more desirably 80X 10 -7 K -1 Is the upper limit. Accordingly, when the optical glass is press-molded using the mold, 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 molding, and the productivity of the optical element can be improved.
The optical glass of the present invention has high visible light transmittance, particularly high transmittance on the short wavelength side of visible light, and therefore is preferably less colored.
In particular, the optical glass of the present invention exhibits a spectral transmittance of 80 wavelength (. Lamda.) in a sample having a thickness of 10mm, if expressed in terms of transmittance of glass 80 ) The upper limit is preferably 450nm, more preferably 420nm, still more preferably 400nm, and still more preferably 380 nm.
In the optical glass of the present invention, the spectral transmittance showed the shortest wavelength (λ) of 5 in a sample having a thickness of 10mm 5 ) The upper limit is preferably 400nm, more preferably 380nm, and still more preferably 350 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 small specific gravity. More specifically, the specific gravity of the optical glass of the present invention is 4.50 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 set to an upper limit of 4.50, more preferably set to an upper limit of 4.20, and still more preferably set to an upper limit of 4.00. The specific gravity of the optical glass of the present invention is generally 3.00 or more, more specifically 3.20 or more, and still more specifically 3.40 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 is preferably resistant to devitrification when producing glass (in the specification, it is sometimes referred to simply as glass having high resistance to devitrification, and is more preferable because it can suppress a decrease in transmittance due to crystallization of glass or the like when producing glass, and therefore it can be preferably applied to an optical element such as a lens that transmits visible light.
[ glass molded article and optical element ]
The optical glass produced can be used to produce a glass molded article by a method such as polishing, reheat press molding, and precision press molding. That is, a glass molded body may be produced by mechanical processing such as grinding and polishing of an optical glass, or by performing a polishing process after reheat press molding of a preform produced from an optical glass, or by performing precision press molding of a preform produced by performing a polishing process and a preform molded by well-known float molding or the like. The method for producing the glass molded article is not limited to these methods.
Thus, the glass molded body formed of the optical glass of the present invention is useful for various optical elements and optical designs, and is particularly preferable for optical elements such as lenses and prisms. Accordingly, a glass molded body having a large diameter can be formed, and therefore, not only can the size of the optical element be increased, but also imaging characteristics and projection characteristics with high definition and high precision can be achieved when the glass molded body is used in an optical device such as a camera or a projector.
[ example ]
The compositions and refractive indices (n) of examples (No. 1 to No. 21) and comparative examples (No. A) of the present invention d ) Abbe number (v) d ) Glass transition temperature (Tg), yield point (At), average linear expansion coefficient (alpha), spectral transmittance of 5% and wavelength of 80% (lambda) 5 、λ 80 ) Specific gravities are shown in tables 1 to 4.
The following embodiments are provided for purposes of illustration and are not limited to these embodiments.
The glasses of examples and comparative examples 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 according to the composition ratios of the examples and comparative 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 1400 ℃ for 35 hours according to the melting difficulty of the glass composition, uniformly stirring the raw materials, defoaming the raw materials, lowering the temperature to 1000 to 1300 ℃, uniformly stirring the raw materials, and then pouring the raw materials into a mold to slowly cool the raw materials.
Refractive index (n) of glasses of examples and comparative examples d ) Abbe number (v) d ) The measurement was performed in accordance with JOGIS08-2003, a Japanese optical nitroprusside Industrial Association standard. In addition, based on the obtained refractive index (n d ) Abbe number (v) d ) The value of (2) is represented by the relation n d ＝a×v d In +b, the intercept b of the inclination a at 0.01 is determined.
The glass used in the measurement was treated with an annealing furnace at a slow cooling rate of-25 ℃/hr.
The glass transition temperatures (Tg) and yield points (At) of the glasses of examples and comparative examples were obtained from thermal expansion curves obtained by measuring the relationship between temperature and elongation of samples according to the Japanese optical nitroprusside Specification Standard JOGIS08-2003 "method for measuring thermal expansion of optical glass".
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 nitroprusside Industrial Association Standard.
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, lambda was obtained by measuring the spectral transmittance of 200800nm of a relatively parallel polished article having a thickness of 10.+ -. 0.1mm according to JIS Z8722 5 (wavelength at 5% transmittance) and lambda 80 (wavelength at 80% transmittance).
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".
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
As shown in the above table, the optical glass of the examples of the present invention is free of expensive components, particularly Ta 2 O 5 Component glasses, which can be obtained at a lower cost.
In addition, the optical glass of the embodiment of the present invention has refractive index (n d ) Are each 1.60 or more, more specifically 1.67 or more, and the refractive index (n d ) Below 1.80, more specifically below 1.70, are within the claimed range.
In addition, the optical glass of the embodiment of the present invention has an Abbe number (v d ) Are each 40 or more, more specifically 52 or more, and the Abbe number (v d ) Below 60, more specifically below 55, are all within the required range.
In addition, the optical glass of the embodiment of the present invention has refractive index (n d ) Abbe number (v) d ) Meets (-0.01 v) d +2.13)≦n d ≦(-0.01v d +2.23), more specifically (-0.01 v) d +2.21)≦n d ≦(-0.01v d +2.25). In addition, regarding the refractive index (n d ) Abbe number (v) d ) As shown in fig. 1.
These optical glasses are stable glasses that are not devitrified.
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 of which are within the required ranges, and an optical glass having high stability can be obtained.
In addition, since the optical glass of the examples of the present invention has a glass transition temperature of 600 ℃ or lower, more specifically 560 ℃ or lower, it is presumed that press molding of glass can be achieved at a lower temperature. The optical glass of the present invention has a yield point of 700 ℃ or lower, more specifically 600 ℃ or lower.
On the other hand, the glass of the comparative example had a glass transition temperature exceeding 600 ℃.
Therefore, it is clear that the optical glass of the example of the present invention has a lower glass transition temperature than the glass of the comparative example, and is preferable for press molding. This can also be inferred from the lower yield point of the optical glass of the examples of the present invention.
Thus, it was found that the optical glass according to the embodiment of the present invention had refractive index (n d ) And Abbe number (vd) are in the required range, the glass transition temperature is lower, the press forming is ideal, and the stability is higher.
In addition, the optical glass of the embodiment of the invention, lambda 80 (wavelength at 80% transmittance) is 450nm or less, more specifically 380nm or less. In addition, the optical glass of the embodiment of the invention, lambda 5 (wavelength at a transmittance of 5%) is 400nm or less, more specifically 330nm or less.
In addition, the optical glass of the embodiment of the present invention 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.
The specific gravity of the optical glass according to the embodiment of the present invention is 4.50 or less, more specifically 3.60 or less. From this, it is also possible to infer that the optical glass of the embodiment of the present invention has a high transmittance for visible light and a low specific gravity and average linear expansion coefficient.
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 various modifications may be made by those skilled in the art without departing from the spirit and scope of the invention.
Claims (11)
1. An optical glass characterized by comprising, in mole% based on oxides, B 2 O 3 More than 44.0% of the components and less than 55.0% of Ln 2 O 3 More than 7.0% and less than 11.0% of the components, wherein Ln is selected from the group consisting of La, gd, Y, yb The number of the selected one or more than 1,
SiO 2 the composition is more than 7.0% and less than 12.5%,
Li 2 the O component is more than 7.0% and less than 13.0%,
ZrO 2 the composition is more than 1.0 percent and less than 5.0 percent,
Ta 2 O 5 the content of the component (A) is less than 1.0%, and the sum of the moles of the oxide basis (ZnO+Li) 2 O) is greater than 25.0% and 40.0% or less, and has a refractive index n of 1.60 to 1.80 d An Abbe number v of 40 to 60 d 。
2. The optical glass according to claim 1, wherein the glass is characterized in that the glass is used for a glass substrate,
La 2 O 3 the components are 0 to 20.0 percent,
Gd 2 O 3 the components are 0 to 10.0 percent,
Y 2 O 3 the components are 0 to 15.0 percent,
Yb 2 O 3 the components are 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,
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 10.0 percent,
ZnO component is 0-25.0%,
TiO 2 the components are 0 to 20.0 percent,
Nb 2 O 5 the components are 0 to 15.0 percent,
WO 3 the components are 0 to 10.0 percent,
P 2 O 5 the components are 0 to 15.0 percent,
GeO 2 the components are 0 to 15.0 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 10.0 percent,
TeO 2 the components are 0 to 15.0 percent,
SnO 2 the components are 0 to 5.0 percent
Sb 2 O 3 The components are 0 to 1.0 percent.
3. An optical glass according to claim 1, wherein the sum of moles of oxide basis (B 2 O 3 +SiO 2 ) 53.0% or more and less than 65.0%.
4. The optical glass according to claim 1, wherein Rn calculated on an oxide basis 2 The sum of the moles of the O components is 20.0% or less, wherein Rn is 1 or more selected from the group consisting of Li, na and K,
the sum of the moles of RO components is 10.0% or less, wherein R is 1 or more selected from the group consisting of Mg, ca, sr, ba.
5. An optical glass according to claim 1, wherein the sum of moles of oxide basis (ro+rn) 2 O) is more than 7.0% and 25.0% or less, wherein Rn is 1 or more selected from the group consisting of Li, na, and K, and R is 1 or more selected from the group consisting of Mg, ca, sr, ba.
6. The optical glass according to claim 1, wherein the molar ratio ZnO/(zno+ro) based on the oxide is 0.50 or more, wherein R is 1 or more selected from the group consisting of Mg, ca, sr, ba.
7. An optical glass according to claim 1, wherein the sum of moles of oxide basis (zno+zro) 2 ) More than 15.0% and less than 35.0%.
8. The optical glass according to claim 1, wherein the glass transition temperature Tg is 600 ℃ or lower.
9. An optical element comprising the optical glass according to any one of claims 1 to 8.
10. Preform, characterized in that it is composed of an optical glass according to any one of claims 1 to 8 and is used for polishing and/or precision press forming.
11. An optical element characterized in that the preform of claim 10 is precision press-worked.
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| JP2014-261300 | 2014-12-24 | ||
| JP2014261300 | 2014-12-24 | ||
| JP2015-218902 | 2015-11-06 | ||
| JP2015218902A JP6689057B2 (en) | 2014-12-24 | 2015-11-06 | Optical glass, preforms and optical elements |
| CN201510963800.8A CN105731789A (en) | 2014-12-24 | 2015-12-21 | Optical glass, prefabricated member and optical element |
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| JP3059719B2 (en) * | 1998-04-28 | 2000-07-04 | ホーヤ株式会社 | Optical glass, materials for precision press molding and optical components using it |
| JP4751225B2 (en) * | 2006-03-28 | 2011-08-17 | Ｈｏｙａ株式会社 | Optical glass, precision press-molding preform, optical element and manufacturing method thereof |
| CN105948483B (en) * | 2010-07-26 | 2020-05-15 | 株式会社小原 | Optical glass, preform and optical element |
| TWI594966B (en) * | 2010-10-08 | 2017-08-11 | Ohara Kk | Optical glass, preform and optical element |
| CN102311228A (en) * | 2011-06-30 | 2012-01-11 | 湖北新华光信息材料有限公司 | Optical glass |
| CN107721160A (en) * | 2013-04-05 | 2018-02-23 | 株式会社小原 | Optical glass, preforming material and optical element |
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