CN117843231A - Phosphate glass, optical glass, and optical element - Google Patents
Phosphate glass, optical glass, and optical element Download PDFInfo
- Publication number
- CN117843231A CN117843231A CN202311259600.5A CN202311259600A CN117843231A CN 117843231 A CN117843231 A CN 117843231A CN 202311259600 A CN202311259600 A CN 202311259600A CN 117843231 A CN117843231 A CN 117843231A
- Authority
- CN
- China
- Prior art keywords
- less
- component
- glass
- still
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000003287 optical effect Effects 0.000 title claims abstract description 24
- 239000005365 phosphate glass Substances 0.000 title claims abstract description 21
- 239000005304 optical glass Substances 0.000 title claims abstract description 15
- 238000002834 transmittance Methods 0.000 claims abstract description 45
- 230000003595 spectral effect Effects 0.000 claims abstract description 11
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims abstract description 10
- 239000011521 glass Substances 0.000 claims description 68
- 239000000203 mixture Substances 0.000 claims description 12
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 abstract description 18
- 238000004031 devitrification Methods 0.000 description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 21
- 229910010413 TiO 2 Inorganic materials 0.000 description 13
- 229910052697 platinum Inorganic materials 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 9
- 238000003303 reheating Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000007496 glass forming Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000010494 opalescence Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical class OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 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
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
The invention provides phosphate glass and optical glass which have good transmissivity before heat treatment, high productivity and excellent transmissivity in a high refractive index region including a wide visible light region with a short wavelength, and an optical element using the optical glass. The phosphate glass has a refractive index (n d ) A spectral transmittance (lambda) of 1.90000 or more 5 ) At 400nm or less, contains more than 0% and less than 1.0% of Li in terms of mass% based on oxide 2 O component, quality and WO 3 +Bi 2 O 3 +Gd 2 O 3 Is 10.0% or less.
Description
Technical Field
The present invention relates to a phosphate glass, an optical glass, and an optical element.
Background
In an optical system requiring high brightness, in order to reduce the load of a light source, it is required that the transmittance of the lens of the optical system on the short wavelength side is excellent. Although the properties required for the optical device used also vary, a glass satisfying various types of requirements is required. In addition, from the viewpoint of reducing the weight of the entire optical device, the weight reduction of the lens is important.
In addition, it is known that a phosphate glass is easily alloyed with platinum, and in the case of melting a phosphate glass, there is a production method in which a raw material is first coarsely melted in a quartz crucible and then melted in a platinum crucible.
In particular, tiO 2 Component, nb 2 O 5 Ingredients, WO 3 Component, bi 2 O 3 The high refractive index component such as the component is a component that is likely to cause coloring due to platinum, that is, a so-called counter-color.
Therefore, in the case where a large amount of high refractive index component is contained in the phosphate glass, a heat treatment step for reducing the counter-color is performed after the glass is manufactured.
Further, phosphate glass having a strong primary color is in a state where the inside of the glass is hardly transparent, and therefore, there is a problem that the inside of the glass is devitrified and texture cannot be confirmed unless the heat treatment step is performed.
Patent document 1 discloses a method of adding Li to a high-dispersion component 2 The light transmittance of the short wave side of the phosphate optical glass cannot be said to be sufficient, and the light weight of the lens cannot be said to be sufficient.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2020-19710
Disclosure of Invention
Technical problem to be solved by the invention
The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a phosphate glass and an optical glass which have excellent transmittance before heat treatment, high productivity, and excellent transmittance in a wide visible light range including a short wavelength, and an optical element using the optical glass.
Method for solving technical problems
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that by adjusting the ratio of glass components, a phosphate glass having a high transmittance before heat treatment and a high productivity and excellent transmittance in a wide visible light range including a short wavelength can be obtained, and have completed the present invention. In particular, the invention provides the following products.
(1) A phosphate glass, wherein,
refractive index (n) d ) Is not less than 1.90000 and is not less than 1.90000,
spectral transmittance (lambda) 5 ) Is at most 400nm in length and has a specific wavelength,
the composition comprises, in mass% based on oxides:
more than 0% and less than 1.0% of Li 2 O component, and
mass and WO 3 +Bi 2 O 3 +Gd 2 O 3 Is 10.0% or less.
(2) The phosphate glass according to (1), wherein the mass ratio Li 2 O.times.100/BaO is 30.0 or less.
(3) The optical glass as described in (1) or (2).
(4) An optical element formed of the glass according to (3).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide a phosphate glass and an optical glass which are excellent in transmittance in a wide visible light range, excellent in transmittance before heat treatment, and high in productivity, and excellent in transmittance in a wide visible light range including a short wavelength, and an optical element using the optical glass.
Detailed Description
Hereinafter, embodiments of the glass of the present invention will be described in detail, and 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, the overlapping portions of the description may be appropriately omitted, and the gist of the invention is not limited.
In the present invention, the transmittance after the heat treatment may be referred to as transmittance, transmittance in the visible region, spectral transmittance, or the like.
[ glass component ]
The following describes the composition ranges of the respective components constituting the glass of the present invention. In the present specification, unless specifically denied, the content of each component is expressed by mass% as compared with the total mass of the glass in terms of oxides. Here, the term "oxide-converted composition" means that the composition of each component contained in the glass is expressed by taking the total mass of the oxide formed as 100 mass% assuming that all of the oxide, complex salt, metal fluoride, and the like used as raw materials of the glass composition component of the present invention are decomposed and become oxide at the time of melting.
The phosphate glass of the present invention is a glass obtained by forming oxides on SiO known as mesh 2 Component (B) 2 O 3 Component, P 2 O 5 Among the components, P 2 O 5 Glass with the largest content of components.
P 2 O 5 The component (c) is a glass-forming component and can provide excellent reheat press formability. Thus, P 2 O 5 The lower limit of the content of the component (a) is preferably 15.0% or more, more preferably 16.0% or more, still more preferably 18.0% or more, and still more preferably 20.0% or more.
On the other hand, by making P 2 O 5 The content of the component (A) is 40.0% or less, and a desired refractive index and Abbe number can be obtained. Thus, P 2 O 5 The upper limit of the content of the component (A) is preferably 40.0% or less, more preferably 35.0% or less, and most preferably 30.0% or less.
Nb 2 O 5 The component (a) is a component capable of increasing the refractive index and decreasing the Abbe number. Thus, nb 2 O 5 The lower limit of the content of the component (A) is preferably 25.0% or more, more preferably 28.0% or more, still more preferably 30.0% or more.
On the other hand, by making Nb 2 O 5 The content of the components is below 60.0%, which can reduce the material cost of the glass and can be mentionedHigh devitrification resistance. Thus, nb 2 O 5 The upper limit of the content of the component is preferably 60.0% or less, more preferably 58.0% or less, still more preferably 55.0% or less, further preferably 53.0% or less, still further preferably 50.0% or less.
TiO 2 The component (a) is a component capable of increasing the refractive index and decreasing the Abbe number. Thus, tiO 2 The lower limit of the content of the component(s) is preferably more than 0%, more preferably 1.5% or more, still more preferably 3.0% or more, and still more preferably 5.0% or more.
On the other hand, by making TiO 2 The content of the component is 30.0% or less, and deterioration of transmittance on the short wavelength side can be suppressed. Thus, tiO 2 The upper limit of the content of the component is preferably 30.0% or less, more preferably 25.0% or less, still more preferably 23.0% or less, and further preferably 20.0% or less.
The BaO component is a component capable of inhibiting platinum from being dissolved. In addition, the BaO component, unlike other alkaline earth metals, is mixed with P 2 O 5 The compatibility of the components is good, and the reheat press formability is excellent. Therefore, the lower limit of the content of the BaO component is preferably more than 0%, more preferably 0.1% or more, still more preferably 0.2% or more, still more preferably 0.5% or more, still more preferably 1.0% or more, still more preferably 2.0% or more.
On the other hand, by setting the content of the BaO component to 25.0% or less, the decrease in refractive index and devitrification of the glass due to the excessive content can be reduced. Therefore, the upper limit of the content of the BaO component is preferably 25.0% or less, more preferably 23.0% or less, still more preferably 20.0% or less, further preferably 18.0% or less, and still further preferably 16.0% or less.
The MgO component, caO component, and SrO component are components that can suppress platinum dissolution, and can adjust the refractive index, meltability, and devitrification resistance of the glass.
On the other hand, by setting the content of the MgO component, caO component, and SrO component to 5.0% or less, it is possible to suppress a decrease in refractive index and to reduce devitrification due to an excessive content of these components. Accordingly, the upper limit of the content of each of the MgO component, caO component, and SrO component is preferably 5.0% or less, more preferably 4.0% or less, still more preferably less than 3.0%, still more preferably 2.0% or less, and still more preferably 1.0% or less.
By making the content of the ZnO component less than 5.0%, the decrease in refractive index can be suppressed, and devitrification due to excessive decrease in viscosity can be reduced. Therefore, the upper limit of the content of the ZnO component is preferably less than 5.0%, more preferably less than 4.0%, still more preferably less than 3.0%, and further preferably 2.0% or less.
Li 2 The O component can reduce the melting temperature of the glass raw material, reduce coloring from the high refractive index component, and can improve the transmittance before heat treatment because coloring from the high refractive index component can be reduced. Thus Li 2 The lower limit of the content of the O component is preferably more than 0%, more preferably 0.01% or more, still more preferably 0.03% or more, and still more preferably 0.05% or more.
Li, on the other hand 2 The upper limit of the content of the O component is preferably less than 1.0%, more preferably 0.8% or less, still more preferably 0.5% or less, and still more preferably 0.3% or less.
Na 2 The O component is a component that can improve the meltability of the glass raw material and can improve the transmittance. Thus, na 2 The lower limit of the content of the O component is preferably more than 0%, more preferably 0.1% or more, still more preferably 0.5% or more, still more preferably 1.0% or more, still more preferably 1.5% or more, still more preferably 2.0% or more.
On the other hand, by making Na 2 The content of the O component is 15.0% or less, and thus, a decrease in refractive index of the glass due to an excessive content can be suppressed, devitrification can be reduced, and devitrification by reheating pressing can be suppressed. Thus, na 2 The upper limit of the content of the O component is preferably 15.0% or less, more preferably 12.0% or less, and still more preferably 10.0% or less.
K 2 The O component is a component which can improve the meltability and can improve the transmittance. Thus, K is 2 The lower limit of the content of the O component is preferably more than 0%, more preferably 0.5% or more, still more preferably more than 1.0%.
On the other hand, by making K 2 The content of the O component is 10.0% or less, whereby the stability of the glass can be maintained and the decrease in refractive index can be suppressed. Thus, K is 2 The upper limit of the content of the O component is preferably 10.0% or less, more preferably 8.0% or less, and still more preferably 5.0% or less.
SiO 2 The component is a glass forming oxide component. In addition, the viscosity of the molten glass can be improved, and the chemical durability can be improved. Thus, siO 2 The lower limit of the content of the component (A) is preferably more than 0%, more preferably 0.1% or more, still more preferably 0.3% or more.
On the other hand, by making SiO 2 The content of the component is 5.0% or less, and the rise of the glass transition point can be suppressed, and the decrease of the refractive index can be suppressed. Thus, siO 2 The upper limit of the content of the component is preferably 5.0% or less, more preferably 4.0% or less, still more preferably 3.0% or less, still more preferably 2.0% or less, still more preferably 1.0% or less, still more preferably 0.8% or less, still more preferably 0.5% or less.
B 2 O 3 The component (A) is a component used as a glass-forming oxide. Thus B 2 O 3 The lower limit of the content of the component(s) is preferably more than 0%, more preferably 0.1% or more, still more preferably 0.2% or more, and still more preferably 0.3% or more.
On the other hand, by making B 2 O 3 The content of the component is 5.0% or less, and deterioration of devitrification at the time of reheating pressing can be reduced, and deterioration of chemical durability can be suppressed. Thus B 2 O 3 The upper limit of the content of the component is preferably 5.0% or less, more preferably 4.0% or less, and still more preferably 3.0% or less.
WO 3 The component (a) is a component capable of improving refractive index and devitrification resistance and reducing Abbe number.
In particular, by making WO 3 Content of the ingredientsWhen the content is 10.0% or less, deterioration of reheat press formability can be suppressed, and decrease in transmittance on the short wavelength side can be suppressed. Thus, WO 3 The upper limit of the content of the component is preferably 10.0% or less, more preferably 8.0% or less, still more preferably 5.0% or less, and still more preferably 3.0% or less.
By making Bi 2 O 3 The content of the component is 5.0% or less, so that the devitrification resistance can be improved, and the decrease in transmittance on the short wavelength side can be suppressed. Therefore, bi 2 O 3 The upper limit of the content of the component is preferably 5.0% or less, more preferably 4.0% or less, still more preferably 3.0% or less, further preferably 2.0% or less, and still further preferably 1.0% or less.
By making Al 2 O 3 The content of the component (A) is 10.0% or less, and the glass raw material can be improved in meltability and devitrification resistance. Thus, al 2 O 3 The upper limit of the content of the component is preferably 10.0% or less, more preferably 8.0% or less, still more preferably 5.0% or less, further preferably 3.0% or less, and still further preferably 1.0% or less.
ZrO 2 The component (c) is a component that can improve the refractive index and the visible light transmittance and can improve the devitrification resistance. ZrO (ZrO) 2 The upper limit of the content of the component is preferably 10.0% or less, more preferably 8.0% or less, still more preferably 5.0% or less, further preferably 3.0% or less, and still further preferably 1.0% or less.
La 2 O 3 Component, Y 2 O 3 Component, gd 2 O 3 Composition and Yb 2 O 3 The component (c) is a component that can improve the refractive index and the visible light transmittance and can improve the chemical durability.
On the other hand, by making La 2 O 3 Component, Y 2 O 3 Component, gd 2 O 3 Composition and Yb 2 O 3 The content of each component is 10.0% or less, the increase in Abbe number can be suppressed, and the devitrification resistance can be improved. Therefore La 2 O 3 Component, Y 2 O 3 Component, gd 2 O 3 Composition and Yb 2 O 3 The upper limit of the content of each component is preferably 10.0% or less, more preferably less than 5.0%, still more preferably 4.0% or less, still more preferably 3.0% or less, still more preferably 2.0% or less, still more preferably 1.0% or less.
GeO 2 The upper limit of the content of the component is preferably 3.0% or less, more preferably 2.0% or less, still more preferably 1.0% or less, further preferably 0.5% or less, and most preferably none.
TeO 2 The upper limit of the content of the component is preferably 3.0% or less, more preferably 2.0% or less, still more preferably 1.0% or less, further preferably 0.5% or less, and most preferably none.
Ta 2 O 5 The upper limit of the content of the component is preferably 3.0% or less, more preferably 2.0% or less, still more preferably 1.0% or less, and still more preferably 0.5% or less.
Ga 2 O 3 The upper limit of the content of the component is preferably 3.0% or less, more preferably 2.0% or less, still more preferably 1.0% or less, further preferably 0.5% or less, and most preferably none.
SnO 2 The upper limit of the content of the component is preferably 3.0% or less, more preferably 1.0% or less, still more preferably 0.5% or less, still more preferably 0.3% or less, still more preferably 0.2% or less, still more preferably 0.1% or less.
Sb 2 O 3 The component (c) is a component capable of promoting defoaming of melted glass.
On the other hand, if Sb 2 O 3 If the content of the component is large, the visible light transmittance is also easily reduced, and alloying with a melting device (particularly, noble metal such as Pt) is easily caused. Thus, sb 2 O 3 The upper limit of the content of the component is preferably 2.0% or less, more preferably 1.0% or less, still more preferably 0.5% or less, still more preferably 0.1% or less, still more preferably 0.05% or less.
The glass was clarified and defoamedNot limited to the above SnO 2 Composition and Sb 2 O 3 As the component, a fining agent, a defoaming agent, or a combination thereof, which are known in the art of glass manufacturing, can be used.
Rn 2 The sum of the contents of the O component (where Rn is 1 or more selected from the group consisting of Li, na, and K) is greater than 0%, and has an effect of improving low-temperature meltability. Thus Rn 2 The sum of the contents of the O components is preferably more than 0%, more preferably 1.0% or more, still more preferably 2.0% or more, still more preferably 3.0% or more, still more preferably 4.0% or more.
On the other hand, rn 2 The sum of the contents of the O component (in the formula, rn is 1 or more selected from the group consisting of Li, na, and K) is preferably 20.0% or less in order to suppress deterioration of the devitrification resistance.
Thus Rn 2 The upper limit of the sum of the contents of the O components is preferably 20.0% or less, more preferably 18.0% or less, still more preferably 15.0% or less, and still more preferably 13.0% or less.
The total content of RO components (where R is at least 1 of MgO, caO, srO and BaO) is preferably at most 25.0% in order to suppress a decrease in refractive index and to reduce devitrification due to an excessive content of these components. Therefore, the upper limit of the mass sum of the RO components is preferably 25.0% or less, more preferably 23.0% or less, still more preferably 20.0% or less, further preferably 18.0% or less, still further preferably 16.0% or less.
On the other hand, the total content of RO components is preferably more than 0% from the viewpoint of suppressing platinum dissolution. Therefore, the total content of RO components is preferably more than 0%, more preferably 0.1% or more, still more preferably 0.2% or more, still more preferably 0.5% or more, still more preferably 1.0% or more, still more preferably 2.0% or more.
By making Ln 2 O 3 The component (wherein Ln is 1 or more selected from the group consisting of La, Y, gd, yb) is 10.0% or less, and can suppress the increase in Abbe number and improve the devitrification resistance. Thus Ln 2 O 3 The sum of the contents of the components is preferably 10.0% or less, more preferably 10.0% or less, still more preferably less than 5.0%, still more preferably 4.0% or less, still more preferably 3.0% or less, still more preferably 2.0% or less, still more preferably 1.0% or less.
By making Li to be compared with the total content of BaO components 2 Mass ratio Li of O component converted to 100 times 2 The O.times.100/BaO is 30.00 or less, and the transmittance of the glass before heat treatment can be improved. Therefore, mass ratio Li 2 The upper limit of O.times.100/BaO is preferably 30.00 or less, more preferably 25.00 or less, and still more preferably 20.00 or less.
On the other hand, mass ratio Li 2 O.times.100/BaO is preferably more than 0 in order to improve the reheat press formability and to suppress platinum dissolution. Therefore, mass ratio Li 2 The lower limit of O.times.10/BaO is preferably more than 0, more preferably 0.0001 or more, still more preferably 0.0005 or more.
WO 3 Component and Bi 2 O 3 Component, gd 2 O 3 The component (c) has an effect of increasing the refractive index, but from the viewpoint of weight reduction of the lens, the content thereof is desirably reduced. Thus, quality and WO 3 +Bi 2 O 3 +Gd 2 O 3 The upper limit thereof is preferably 10.0% or less, more preferably 7.0% or less, still more preferably 5.0% or less, still more preferably 4.5% or less, still more preferably 4.0% or less, still more preferably 3.5% or less, still more preferably 3.0% or less, still more preferably 2.5% or less, still more preferably 2.0% or less.
With TiO 2 Component (A) and Nb 2 O 5 Ingredients, WO 3 Component, bi 2 O 3 Nb in the total content of the components 2 O 5 Mass ratio of components Nb 2 O 5 /(TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 ) Preferably greater than 0.Nb (Nb) 2 O 5 The component is similar to TiO with high refractive index and high dispersion 2 Ingredients, WO 3 Component, bi 2 O 3 The component is the most favorable component for transmittance on the short wavelength side when compared. Therefore, mass ratio Nb 2 O 5 /(TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 ) The lower limit thereof is preferably greater than 0, more preferably 0.05 or more, still more preferably 0.10 or more, still more preferably 0.20 or more, still more preferably 0.30 or more, still more preferably 0.40 or more, still more preferably 0.50 or more, still more preferably 0.53 or more, still more preferably 0.55 or more, still more preferably 0.58 or more.
On the other hand, by making the mass ratio Nb 2 O 5 /(TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 ) The glass stability can be maintained at 1.00 or less. Therefore, mass ratio Nb 2 O 5 /(TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 ) The upper limit is preferably 1.00 or less, more preferably 0.95 or less, and further preferably 0.90 or less.
With BaO component and K 2 TiO with a total O content of 2 Mass ratio of the contents of the components TiO 2 /(BaO+K 2 O), preferably 0.15 to 5.0. By making mass ratio TiO 2 The transmittance in the visible region can be improved by the ratio/(bao+k2o) of 0.15 to 5.0. Therefore, mass ratio TiO 2 /(BaO+K 2 O), the lower limit thereof is preferably 0.15 or more, more preferably 0.18 or more, still more preferably 0.20 or more, and further preferably 0.22 or more. On the other hand, mass ratio TiO 2 /(BaO+K 2 O), the upper limit thereof is preferably 5.00 or less, more preferably 4.80 or less, still more preferably 4.50 or less.
< concerning the component which should not be contained >)
Next, the components that should not be contained in the glass of the present invention, and preferably, the components that should not be contained are described.
Other components not described above may be added as necessary within a range not impairing the characteristics of the glass of the present invention. However, when each of the various transition metal components such as Ce, V, cr, mn, fe, co, ni, cu, ag and Mo is contained alone or in combination, even if the content is small, the glass is colored and the effect of the present invention of improving the visible light transmittance is canceled by absorbing the wavelength in the visible light region, and therefore, it is preferable that the transition metal components are not actually contained in the glass that transmits the wavelength in the visible light region.
In addition, lead compounds such As PbO and As 2 O 3 The arsenic compound is preferably substantially not contained, that is, not contained at all except for unavoidable contamination, because it is a component that is highly burdened with the environment.
Further, since Th, cd, tl, os, be and Se components have a tendency to be avoided as harmful chemicals in recent years, in the case of using these components, environmental measures are required not only in the glass manufacturing step but also in the processing step and up to the disposal after production. Therefore, in the case where environmental impact is important, it is preferable that these components are not substantially contained.
[ method of production ]
The glass of the present invention can be produced, for example, as follows. For example, the above raw materials are uniformly mixed so that the respective components are within a predetermined content range, and the produced mixture is placed in a platinum crucible, a quartz crucible, or an alumina crucible, and then is placed in the platinum crucible, the platinum alloy crucible, or the iridium crucible, and is melted in a temperature range of 1000 to 1350 ℃ for 1 to 10 hours, and then is stirred to be homogenized, defoamed, and the like, and then is reduced to a temperature of 1250 ℃ or less, and then is subjected to fine stirring to remove textures, and is cast into a mold, and then is slowly cooled, thereby producing the alloy. The resultant glass may be subjected to a heat treatment at 550 to 700 ℃ for 1 to 50 hours, depending on the components.
Physical Properties
The glass of the present invention preferably has a desired refractive index. More specifically, the refractive index (n d ) The lower limit is preferably 1.90000 or more, more preferably 1.90300 or more, and still more preferably 1.90500 or more. Thereby, the degree of freedom in optical design is increasedThe device is wide, and can obtain a large light refraction amount while realizing the thinning of the device. The refractive index (n d ) The upper limit of (2) is not particularly limited, but is preferably 2.00000 or less, more preferably 1.99000 or less, still more preferably 1.98000 or less, still more preferably 1.97000 or less, still more preferably 1.96000 or less.
In addition, the glass of the present invention is required to have a desired dispersion (Abbe number). In particular, the Abbe number (. Nu.) of the glass of the invention d ) The lower limit thereof is preferably 15.00 or more, more preferably 16.00 or more, still more preferably 17.00 or more. On the other hand, abbe number (. Nu.) of glass d ) The upper limit thereof is preferably 25.00 or less, more preferably 22.50 or less, still more preferably 22.00 or less. This can greatly widen the degree of freedom in optical design when the glass of the present invention is used as an optical element.
In addition, the glass of the present invention is preferably less colored before heat treatment. In particular, the glass of the present invention, when expressed in terms of transmittance of glass, a sample having a thickness of 10mm shows a wavelength (LH lambda) at a spectral transmittance of 70% 70 ) The upper limit is preferably 1060nm or less, more preferably 1050nm or less, and still more preferably 1040nm or less. In addition, the wavelength (LH λ) at which the spectral transmittance of 5% is shown 5 ) The upper limit is preferably 410nm or less, more preferably 408nm or less, and still more preferably 405nm or less. Accordingly, since the internal quality of glass such as devitrification and texture can be checked before the heat treatment, glass having a poor internal quality can be found in advance, and productivity can be improved.
In addition, the glass of the present invention is preferably less colored. In particular, the glass of the present invention, when expressed in terms of transmittance of glass, a sample having a thickness of 10mm shows a wavelength (λ) at which the spectral transmittance is 70% 70 ) The upper limit is preferably 480nm or less, more preferably 470nm or less, and still more preferably 450nm or less. In addition, the wavelength (λ) at which the spectral transmittance of 5% is shown 5 ) The upper limit is preferably 400nm or less, more preferably 398nm or less, still more preferably 395nm or less. Thus, since the absorption edge of the glass is located in or near the ultraviolet region, and is visibleSince the transparency of the glass in the light region is improved, the glass can be preferably used as an optical element such as a lens.
[ optical element ]
The glass of the present invention can be used for various optical elements and optical designs, and particularly preferably, the glass of the present invention is used for manufacturing various optical elements such as lenses, prisms, mirrors, diffraction gratings, and substrates for diffraction gratings by precision press molding. Thus, when used in an optical device such as a camera or a projector that transmits light in the visible region through an optical element, the imaging characteristics can be realized with high definition and high accuracy, and the optical system in the optical device can be miniaturized.
[ example ]
The components and refractive indices (n) of the glasses of examples 1 to 24 and comparative examples 1 to 2 of the present invention d ) Abbe number (v) d ) Wavelengths (LH lambda) showing spectral transmittance of 5% and 70% before heat treatment 5 、LHλ 70 ) Wavelength (λ) showing spectral transmittance of 5% and 70% after heat treatment 5 、λ 70 ) Tables 1 to 4 show the results. The following embodiments are merely examples, and are not limited to these embodiments.
The glasses of examples and comparative examples were prepared by selecting, as raw materials of each component, high-purity raw materials used for general optical glasses such as oxides, carbonates, nitrates, fluorides, hydroxides, and metaphosphoric acid compounds corresponding thereto, weighing and uniformly mixing these raw materials in such a manner as to be the ratio of the compositions of each example shown in the table, charging them into a quartz crucible or a platinum crucible, melting them for 1 to 3 hours at a temperature range of 1000 to 1300 ℃ by using an electric furnace according to the melting difficulty of the glass components, homogenizing them by stirring, defoaming, etc., reducing them to a temperature of 1200 ℃ or lower, finally stirring to remove textures, casting them in a mold, and cooling them slowly. The resultant glass is subjected to a heat treatment at 550 to 700 ℃ for 1 to 30 hours, depending on the components.
Refractive indices and Abbe numbers of glasses of examples and comparative examples, and partial dispersion ratios (θg, F), were in accordance with JIS B7071-2: the V block method specified in 2018. Here, refractive index (n d ) Expressed as a measurement of d-line (587.56 nm) from helium lamp. Further, abbe number (. Nu.d) was measured using the refractive index (n) of the d-line to helium lamp d ) Refractive index (n) of F line (486.13 nm) to hydrogen lamp F ) Refractive index (n) to C line (656.27 nm) C ) According to Abbe number (v) d )＝[(n d －1)/(n F －n C )]Is calculated by the equation (C). These refractive indices (n d ) Abbe number (v) d ) Is obtained by measuring glass obtained by setting the slow cooling rate to-25 ℃/hr.
The transmittance of the glass before and after the heat treatment of examples and comparative examples was measured based on the Japanese optical glass industry Condition Standard (measuring method of the coloration degree of JOGIS05-2019 optical glass). In the present invention, the presence or absence and the degree of coloration of the glass can be determined by measuring the transmittance of the glass. Specifically, according to JIS Z8722, the spectral transmittance of 200 to 2500nm of a face-to-face parallel polishing material having a thickness of 10.+ -. 0.1mm was measured to determine λ 70 (wavelength at 70% transmittance) and lambda 5 (wavelength at 5% transmittance).
[ Table 1 ]
| Mass percent of | SiO 2 | B 2 O 3 | P 2 O 5 | Li 2 O | Na 2 O | K 2 O | M g O | BaO | ZnO | TiO 2 | ZrO 2 | Nb 2 O 5 | WO 3 | Sb 2 O 3 | Totals to |
| Example 1 | 0.49 | 0.49 | 24.75 | 0.19 | 9.89 | 0.00 | 0.00 | 3.82 | 0.00 | 12.86 | 0.00 | 47.51 | 0.00 | 0.01 | 100.0 |
| Example 2 | 0.41 | 2.42 | 19.60 | 0.08 | 0.00 | 3.93 | 0.00 | 20.80 | 0.00 | 6.06 | 0.00 | 44.70 | 2.00 | 0.00 | 100.0 |
| Example 3 | 0.47 | 0.80 | 23.47 | 0.21 | 6.59 | 4.00 | 0.00 | 5.98 | 0.00 | 11.01 | 0.00 | 47.47 | 0.00 | 0.00 | 100.0 |
| Example 4 | 0.00 | 1.99 | 24.93 | 0.10 | 3.22 | 3.94 | 0.00 | 6.53 | 0.00 | 11.53 | 0.00 | 47.76 | 0.00 | 0.00 | 100.0 |
| Example 5 | 0.00 | 1.99 | 24.93 | 0.10 | 3.22 | 3.94 | 0.00 | 6.53 | 1.00 | 12.53 | 0.00 | 45.76 | 0.00 | 0.00 | 100.0 |
| Example 6 | 0.00 | 1.99 | 24.93 | 0.10 | 3.22 | 3.94 | 1.00 | 6.53 | 0.00 | 12.53 | 0.00 | 45.76 | 0.00 | 0.00 | 100.0 |
| Example 7 | 0.49 | 0.49 | 24.75 | 0.19 | 9.89 | 0.00 | 0.00 | 3.82 | 0.00 | 12.86 | 0.00 | 47.51 | 0.00 | 0.01 | 100.0 |
| Example 8 | 0.49 | 0.49 | 24.75 | 0.19 | 9.89 | 0.00 | 0.00 | 3.82 | 0.00 | 12.86 | 0.00 | 47.51 | 0.00 | 0.01 | 100.0 |
| Example 9 | 0.00 | 1.99 | 24.93 | 0.10 | 3.22 | 3.94 | 0.00 | 6.53 | 0.00 | 12.53 | 0.00 | 46.76 | 0.00 | 0.00 | 100.0 |
| Example 10 | 0.00 | 1.99 | 24.93 | 0.10 | 3.22 | 3.94 | 0.00 | 8.53 | 0.00 | 14.53 | 0.00 | 42.76 | 0.00 | 0.00 | 100.0 |
| Example 11 | 0.00 | 1.99 | 24.93 | 0.10 | 3.22 | 3.94 | 0.00 | 10.53 | 0.00 | 16.53 | 0.00 | 38.76 | 0.00 | 0.00 | 100.0 |
| Example 12 | 0.00 | 1.99 | 24.93 | 0.10 | 3.22 | 3.94 | 0.00 | 12.53 | 0.00 | 18.53 | 0.00 | 34.76 | 0.00 | 0.00 | 100.0 |
| Example 13 | 0.00 | 1.99 | 24.93 | 0.10 | 3.22 | 3.94 | 0.00 | 14.53 | 0.00 | 20.53 | 0.00 | 30.76 | 0.00 | 0.00 | 100.0 |
| Example 14 | 0.00 | 1.98 | 24.84 | 0.45 | 3.21 | 3.93 | 0.00 | 6.51 | 0.00 | 12.49 | 0.00 | 46.60 | 0.00 | 0.00 | 100.0 |
| Example 15 | 0.00 | 1.98 | 24.77 | 0.75 | 3.20 | 3.91 | 0.00 | 6.49 | 0.00 | 12.45 | 0.00 | 46.46 | 0.00 | 0.00 | 100.0 |
| Comparative example 1 | 0.00 | 0.00 | 26.94 | 0.33 | 0.00 | 3.28 | 0.00 | 0.00 | 0.00 | 26.18 | 0.00 | 31.92 | 11.35 | 0.00 | 100.0 |
| Comparative example 2 | 0.00 | 2.50 | 21.50 | 0.00 | 0.00 | 2.00 | 0.00 | 20.50 | 0.00 | 16.00 | 0.00 | 37.50 | 0.00 | 0.00 | 100.0 |
[ Table 2 ]
[ Table 3 ]
| Mass percent of | SiO 2 | B 2 O 3 | P 2 O 5 | Li 2 O | Na 2 O | K 2 O | MgO | BaO | ZnO | TiO 2 | ZrO 2 | Nb 2 O 5 | WO 3 | Sb 2 O 3 | Totals to |
| Example 16 | 0.15 | 2.04 | 24.92 | 0.68 | 1.05 | 4.63 | 0.00 | 8.15 | 0.00 | 11.07 | 0.00 | 47.30 | 0.00 | 0.00 | 100.0 |
| Example 17 | 0.48 | 2.07 | 25.35 | 0.69 | 1.07 | 4.71 | 0.00 | 7.27 | 0.00 | 9.21 | 0.00 | 49.15 | 0.00 | 0.00 | 100.0 |
| Example 18 | 0.56 | 2.08 | 24.91 | 0.10 | 0.00 | 6.23 | 0.00 | 6.81 | 0.00 | 8.52 | 0.00 | 49.78 | 0.00 | 0.00 | 100.0 |
| Example 19 | 0.49 | 2.25 | 22.51 | 0.35 | 0.00 | 3.46 | 0.00 | 16.99 | 0.00 | 5.96 | 0.00 | 48.00 | 0.00 | 0.00 | 100.0 |
| Example 20 | 0.51 | 2.36 | 23.11 | 0.46 | 0.00 | 3.56 | 0.00 | 15.24 | 0.00 | 6.62 | 0.00 | 48.14 | 0.00 | 0.00 | 100.0 |
| Example 21 | 0.74 | 2.65 | 23.54 | 0.17 | 0.00 | 3.97 | 0.00 | 13.39 | 0.00 | 7.27 | 0.00 | 48.28 | 0.00 | 0.00 | 100.0 |
| Example 22 | 0.49 | 2.25 | 22.51 | 0.35 | 0.00 | 0.96 | 0.00 | 20.49 | 0.00 | 5.96 | 0.00 | 47.00 | 0.00 | 0.00 | 100.0 |
| Example 23 | 0.51 | 2.36 | 23.41 | 0.16 | 0.00 | 3.56 | 0.00 | 14.74 | 0.00 | 6.62 | 0.00 | 48.64 | 0.00 | 0.00 | 100.0 |
| Example 24 | 0.74 | 2.65 | 23.54 | 0.57 | 0.00 | 3.57 | 0.00 | 13.39 | 0.00 | 7.27 | 0.00 | 48.28 | 0.00 | 0.00 | 100.0 |
[ Table 4 ]
The results of visual confirmation of the presence or absence of devitrification and opalescence before and after the reheating test for the glasses of examples 2, 9, 10 and comparative example 1 are shown in table 5. Here, the devitrification before and after the reheating test and the opalescence were confirmed as follows: a test piece of 15 mm.times.15 mm.times.30 mm was placed on a concave refractory, then placed in an electric furnace, and heated again to a reheating temperature, kept at that temperature for 30 minutes, cooled to room temperature, taken out of the furnace, and 2 surfaces thereof were polished to a thickness of 10mm so that the inside could be observed, and then the presence or absence of devitrification and opalescence in the polished glass sample was visually observed. At this time, the glass which is not devitrified or milky white at the reheating temperature is referred to as good, and the glass which is devitrified or milky white is referred to as good. The reheating temperature is in the range of (Tg+100 to 120 ℃).
[ Table 5 ]
Phosphate glass of examples of the invention, (lambda) 5 ) 400nm or less, in a desired range.
The phosphate glass of the example of the present invention has good transmittance before heat treatment and falls within a desired range.
In addition, the phosphate glass of the example of the present invention was excellent in reheat moldability because it was not devitrified before and after the reheat test. The glass having high formability is reheated, and devitrification due to reheating is reduced, so that the glass has an improved yield and an improved productivity.
As is clear from the above, the phosphate glass of the example of the present invention has a high refractive index, excellent transmittance in a wide visible light range, excellent transmittance before heat treatment, and high productivity.
Although the present invention has been described in detail for the purpose of illustration, the present embodiment is only for the purpose of illustration, and it should be fully understood that many changes may be made to the invention by those skilled in the art without departing from the spirit and scope of the invention.
Claims (4)
1. A phosphate glass, wherein,
refractive index (n) d ) Is not less than 1.90000 and is not less than 1.90000,
spectral transmittance (lambda) 5 ) Is at most 400nm in length and has a specific wavelength,
the composition comprises, in mass% based on oxides:
more than 0% and less than 1.0% of Li 2 O component, and
mass and WO 3 +Bi 2 O 3 +Gd 2 O 3 Is 10.0% or less.
2. The phosphate glass according to claim 1, wherein the mass ratio Li 2 O.times.100/BaO is 30.0 or less.
3. An optical glass as claimed in claim 1 or 2.
4. An optical element formed from the glass of claim 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022-161891 | 2022-10-06 | ||
| JP2023130041A JP2024055765A (en) | 2022-10-06 | 2023-08-09 | Phosphate glass, optical glass, and optical elements |
| JP2023-130041 | 2023-08-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117843231A true CN117843231A (en) | 2024-04-09 |
Family
ID=90535389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311259600.5A Pending CN117843231A (en) | 2022-10-06 | 2023-09-27 | Phosphate glass, optical glass, and optical element |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117843231A (en) |
-
2023
- 2023-09-27 CN CN202311259600.5A patent/CN117843231A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI541213B (en) | Optical glass, preform and optical element | |
| WO2011016566A1 (en) | Optical glass | |
| CN113292242B (en) | Special dispersion optical glass | |
| JP7195040B2 (en) | Optical glass, preforms and optical elements | |
| CN109970337B (en) | Optical glass, glass preform, optical element and optical instrument | |
| WO2012133420A1 (en) | Optical glass, preform, and optical element | |
| TWI777931B (en) | Optical glass, preforms and optical components | |
| TW201620847A (en) | Optical glass, preform and optical element | |
| CN112142322B (en) | Optical glass, glass preform, optical element and optical instrument | |
| JP2022167990A (en) | Optical glass, preform and optical element | |
| JP2023017903A (en) | Optical glass and optical element | |
| CN111977970B (en) | Optical glass and optical element | |
| JP7064282B2 (en) | Optical glass, preforms and optical elements | |
| JP7064283B2 (en) | Optical glass, preforms and optical elements | |
| JP2012206891A (en) | Optical glass, perform, and optical device | |
| JP2012197211A (en) | Optical glass, preform and optical element | |
| CN115028353A (en) | Optical glass having negative anomalous dispersion | |
| CN112028473B (en) | Optical glass for precision mould pressing | |
| CN112028472B (en) | Optical glass, optical element and optical instrument | |
| WO2012133421A1 (en) | Optical glass, preform and optical element | |
| TW201726573A (en) | Optical glass, preform and optical element having an index of refraction (nd) and abbe number ([nu]d) in a desired range and a smaller partial dispersion ratio ([theta]g,F) | |
| CN117843231A (en) | Phosphate glass, optical glass, and optical element | |
| JP7126350B2 (en) | Optical glass, optical elements and preforms | |
| JP2012206892A (en) | Optical glass, perform, and optical device | |
| JP6163620B1 (en) | Optical glass and optical element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication |