CN104129918B - Optical glass, preform, and optical element - Google Patents
Optical glass, preform, and optical element Download PDFInfo
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- CN104129918B CN104129918B CN201410183617.1A CN201410183617A CN104129918B CN 104129918 B CN104129918 B CN 104129918B CN 201410183617 A CN201410183617 A CN 201410183617A CN 104129918 B CN104129918 B CN 104129918B
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Abstract
The invention provides an optical glass, a preform and an optical element, which can obtain the optical glass with refractive index (nd) in a desired range, small abbe number (vd) and partial dispersion ratio (theta g, F) and high visible light transmittance at lower cost. The optical glass contains 10.0 to 40.0 mass% of SiO2Component (b), 5.0% to 50.0% Nb2O5A component having an Abbe's number (vd) of 25 to 35 inclusive, a relationship of (-0.00162 x vd +0.63622) ≦ theta g, F) ≦ 0.00275 x vd +0.68125 being satisfied in a range where vd is not more than 31 between a partial dispersion ratio (theta g, F) and the Abbe's number (vd)>The range of 31 satisfies the relation of (-0.00162 x ν d +0.63622) ≦ (θ g, F) ≦ (0.00162 x ν d + 0.64622).
Description
Technical Field
The invention relates to an optical glass, a preform and an optical element.
Background
Optical systems of digital cameras, video cameras, and the like include color bleeding called aberration, although the size of the optical systems varies. The aberration is classified into monochromatic aberration and chromatic aberration, and particularly, chromatic aberration strongly depends on the material characteristics of a lens used in an optical system.
In general, chromatic aberration is corrected by combining a low-dispersion convex lens and a high-dispersion concave lens, but the combination can correct only aberration in the red region and the green region, and aberration in the blue region remains. The aberration of this blue region that cannot be completely removed is called a secondary spectrum. In order to correct the secondary spectrum, optical design needs to be performed in consideration of the movement direction of g-rays (435.835nm) in the blue region. At this time, the partial dispersion ratio (θ g, F) is used as an index of optical characteristics of interest in optical design. In the optical system in which the low dispersion lens and the high dispersion lens are combined, the secondary spectrum can be corrected favorably by using an optical material having a large partial dispersion ratio (θ g, F) for the low dispersion lens and an optical material having a small partial dispersion ratio (θ g, F) for the high dispersion lens.
The partial dispersion ratio (θ g, F) is represented by the following formula (1).
θg,F＝(ng-nF)/(nF-nC)······(1)
In the optical glass, a partial dispersion ratio (θ g, F) indicating partial dispersibility in a short-wavelength region and an abbe number (ν d) have a substantially linear relationship. The straight line showing this relationship is represented by a straight line connecting 2 points, which draw the partial dispersion ratio and abbe number of NSL7 and PBM2, on a rectangular coordinate with the vertical axis representing the partial dispersion ratio (θ g, F) and the horizontal axis representing the abbe number (ν d), and is referred to as a reference line (see fig. 1). The standard glass as a reference line differs depending on each optical glass manufacturer, but each company is defined with substantially the same slope and intercept. (NSL7 and PBM2 are optical glasses manufactured by Mitsui Kabushiki Kaisha, PBM2 has an Abbe number (. nu.d) of 36.3, a partial dispersion ratio (. theta.g, F) of 0.5828, NSL7 has an Abbe number (. nu.d) of 60.5, and a partial dispersion ratio (. theta.g, F) of 0.5436.)
As a glass having an abbe number (ν d) of 25 or more and 35 or less, for example, optical glasses as shown in patent documents 1 to 3 are known.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-213554
Patent document 2: japanese laid-open patent publication No. 2012-006788
Patent document 3: japanese laid-open patent publication No. 2009-179522
Disclosure of Invention
Problems to be solved by the invention
However, the glasses disclosed in patent documents 1 to 3 have a partial dispersion ratio not small enough to be used as a lens for correcting the secondary spectrum.
In order to reduce the material cost of the optical glass, it is desirable that the raw materials of the respective components constituting the optical glass are as inexpensive as possible. However, the glasses described in patent documents 1 to 3 are difficult to sufficiently meet such a demand.
The present invention has been made in view of the above problems, and an object of the present invention is to obtain an optical glass having a refractive index (nd) within a desired range, a small abbe number (ν d) and a small partial dispersion ratio (θ g, F), and a high transmittance for visible light at a lower cost.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that the use of SiO in combination is effective2Component (b) and other components in a predetermined range, thereby increasing material cost even if Nb is added2O5The content of the component(s) is reduced, and a high refractive index, a low Abbe number (high dispersion), and a low partial dispersion ratio can be obtained, and the visible light transmittance of the glass is improved and the devitrification of the glass is reduced, thereby completing the present invention.
In particular, the present inventors have found that SiO is used in combination2These effects can be obtained by adjusting the contents of the component (A) and the BaO component to predetermined ranges.
Further, the present inventors have found that by using SiO2These effects can be obtained by adjusting the contents of the components and CaO component to be within predetermined ranges and the contents of the other components.
Specifically, the present invention provides the following.
(1) An optical glass containing 10.0 to 40.0 mass% of SiO2Component (b), 5.0% to 50.0% Nb2O5A component having an Abbe's number (vd) of 25 to 35 inclusive, a relationship of (-0.00162 x vd +0.63622) ≦ theta g, F) ≦ 0.00275 x vd +0.68125 being satisfied in a range where vd is not more than 31 between a partial dispersion ratio (theta g, F) and the Abbe's number (vd)>31 range (a)The relation of (-0.00162 x ν d +0.63622) to (theta g, F) to (0.00162 x ν d +0.64622) is satisfied within the enclosure.
(2) The optical glass according to the item (1), wherein the content of the BaO component is 50.0% by mass or less.
(3) The optical glass according to (1) or (2), wherein the BaO component is contained in an amount of 1.0% by mass or more and 50.0% by mass or less.
(4) The optical glass according to any one of (1) to (3), wherein Li is contained in mass%2The content of the O component is 10.0% or less.
(5) The optical glass according to any one of (1) to (4), wherein the content of the CaO component is 30.0% by mass or less.
(6) The optical glass according to any one of (1) to (5), wherein the glass composition comprises, in mass%,
0 to 20.0% of MgO component,
The SrO content is 0-25.0%.
(7) The optical glass according to any one of (1) to (6), wherein the sum by mass of (MgO + CaO + SrO) is 30.0% or less.
(8) The optical glass according to any one of (1) to (7), wherein the glass composition comprises, in mass%,
Na20 to 20.0% of O component,
K2The content of O is0 to 15.0%.
(9) The optical glass according to any one of (1) to (8), wherein Rn2The sum of the mass of the O components is 20.0% or less, and Rn is represented by the formula2In O, Rn is 1 or more selected from the group consisting of Li, Na, K and Cs.
(10) The optical glass according to any one of (1) to (9), wherein ZrO is contained in an amount of 1.0% by mass or more and 15.0% by mass or less2Component (A), containing more than 0% and 20.0% or less of TiO2And (3) components.
(11) The optical glass according to any one of (1) to (10), wherein ZrO is present in a mass ratio2/Nb2O5Is 0.10 to 3.00 inclusive.
(12) According to (1)1) The optical glass according to any of the above, wherein WO is defined in mass%3The content of the component is 20.0% or less.
(13) The optical glass according to any one of (1) to (12), wherein the sum of mass is (TiO)2+Nb2O5+WO3) Is 10.0% or more and 50.0% or less.
(14) The optical glass according to any one of (1) to (13), wherein B is in mass%2O3The content of the component is 15.0% or less.
(15) The optical glass according to any one of (1) to (14), wherein the glass composition comprises, in mass%,
La2 O 30 to 15.0 percent of components,
Gd2O30 to 10.0 percent of components,
Y2O30 to 10.0 percent of components,
Yb2O30 to 10.0 percent of components,
Lu2O3The content of the components is 0-10.0%.
(16) The optical glass according to any one of (1) to (15), wherein the mass sum (B)2O3+La2O3) Is 20.0% or less.
(17) The optical glass according to any one of (1) to (16), wherein the glass composition comprises, in mass%,
Al2O30 to 15.0 percent of components,
0 to 10.0% of ZnO,
GeO20 to 10.0 percent of components,
Ga2 O 30 to 10.0 percent of components,
P2O50 to 10.0 percent of components,
Ta2O50 to 10.0 percent of components,
Bi2O30 to 10.0 percent of components,
Sb2O3The component is 0-1.0%.
(18) The optical glass according to any one of (1) to (17), which has a refractive index (nd) of 1.70 or more and 1.95 or less.
(19) The optical glass according to any one of (1) to (18), wherein the spectral transmittance is represented by a wavelength (λ) of 70%70) Is 450nm or less.
(20) A preform for polishing and/or precision press molding, which is formed from the optical glass according to any one of (1) to (19).
(21) An optical element obtained by grinding and/or polishing the optical glass according to any one of (1) to (19).
(22) An optical element obtained by precision press molding the optical glass according to any one of (1) to (19).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, an optical glass having a refractive index (nd) within a desired range, a small abbe number (ν d) and a small partial dispersion ratio (θ g, F), and a high transmittance for visible light can be obtained at a lower cost.
Drawings
Fig. 1 is a diagram showing a reference line expressed in rectangular coordinates with a partial dispersion ratio (θ g, F) as a vertical axis and an abbe number (vd) as a horizontal axis.
Fig. 2 is a diagram showing a relationship between a partial dispersion ratio (θ g, F) and an abbe number (ν d) in an example of the present application.
Detailed Description
The optical glass of the present invention contains 10.0% to 40.0% by mass of SiO2Component (b), 5.0% to 50.0% Nb2O5A component having an Abbe's number (vd) of 25 to 35 inclusive, a relationship of (-0.00162 x vd +0.63622) ≦ theta g, F) ≦ 0.00275 x vd +0.68125 being satisfied in a range where vd is not more than 31 between a partial dispersion ratio (theta g, F) and the Abbe's number (vd)>The range of 31 satisfies the relation of (-0.00162 x ν d +0.63622) ≦ (θ g, F) ≦ (0.00162 x ν d + 0.64622). By adding Nb2O5The content of the components is reduced to the standardWithin a certain range, thereby reducing expensive Nb2O5The amount of the component used, and therefore the material cost of the optical glass is reduced. By using SiO in combination2Component (b) and BaO component, and the contents thereof are set within predetermined ranges, thereby increasing the material cost even if Nb is added2O5The content of the component is reduced, and the high refractive index, the low Abbe number (high dispersion) and the low partial dispersion ratio can be obtained, thereby improving the visible light transmittance of the glass and reducing the devitrification of the glass.
In particular, the No.1 optical glass contains 10.0% to 40.0% by mass of SiO2Component (b), 5.0% to 50.0% Nb2O5A component, a BaO component of 1.0% to 50.0%, an Abbe number (vd) of 25 to 35, and a partial dispersion ratio (θ g, F) and the Abbe number (vd) satisfy the above-mentioned relationship. By using SiO in combination2Component (b) and BaO component, and their contents are set within a predetermined range, thereby increasing material cost even if Nb is added2O5The content of the component is reduced, and the high refractive index, the low Abbe number (high dispersion) and the low partial dispersion ratio can be obtained, thereby improving the visible light transmittance of the glass and reducing the devitrification of the glass.
The No. 2 optical glass contains 10.0 to 40.0% by mass of SiO2Component (b), 5.0% to 50.0% Nb2O5A component (B) containing 30.0% or less of CaO component, having an Abbe number (ν d) of 25 to 35 inclusive, and satisfying the above-mentioned relationship between the partial dispersion ratio (θ g, F) and the Abbe number (ν d). By mixing SiO2The contents of the component and CaO component are set within predetermined ranges and the contents of the other components are adjusted so as to increase the material cost even though Nb is added2O5The content of the component is reduced, and the high refractive index, the low Abbe number (high dispersion) and the low partial dispersion ratio can be obtained, thereby improving the visible light transmittance of the glass and reducing the devitrification of the glass.
Thus, according to the optical glass of the present invention, an optical glass having a refractive index (nd) within a desired range, a small abbe number (ν d), a small partial dispersion ratio (θ g, F), and a high transmittance for visible light, and a preform and an optical element using the same can be obtained at a lower cost.
The optical glass of the present invention is obtained by the following steps, which are not intended to limit the scope of the present invention. Note that, although description may be omitted where appropriate for overlapping description, the present invention is not limited thereto.
[ glass composition ]
The compositional ranges of the respective components constituting the optical glass of the present invention are described below. In the present specification, unless otherwise specified, the contents of the respective components are all expressed in mass% with respect to the total mass of the glass in terms of oxides. Here, the "oxide-converted composition" means: when all of the oxides, complex salts, metal fluorides, and the like used as raw materials of the glass constituent components of the present invention are decomposed at the time of melting to become oxides, the compositions of the respective components contained in the glass are expressed by taking the total mass of the formed oxides as 100 mass%.
< essential Components, optional Components >
SiO2The component (a) is an essential component for promoting the formation of a stable glass and reducing devitrification (generation of crystals) which is not preferable as an optical glass.
In particular, by using SiO2The content of the component (a) is 10.0% or more, and thus glass having excellent devitrification resistance can be obtained without greatly increasing the partial dispersion ratio of the glass. Further, devitrification and coloration at the time of reheating can be reduced. Thus, SiO2The content of component (c) is preferably 10.0% as the lower limit, more preferably 12.0% as the lower limit, and further preferably 14.0% as the lower limit.
On the other hand, by mixing SiO2The content of the component is 40.0% or less, so that the refractive index of the glass is not easily lowered, and thus a desired high refractive index can be easily obtained and an increase in the partial dispersion ratio of the glass can be suppressed. Further, the meltability of the glass can be maintained well. Thus, SiO2Content of the ingredientsThe upper limit is preferably 40.0%, more preferably 30.0%, and still more preferably 26.0%.
SiO2Component (B) As a raw material, SiO can be used2、K2SiF6、Na2SiF6And the like.
Nb2O5The component (B) is an essential component which can improve the devitrification resistance of the glass, increase the refractive index of the glass, and reduce the Abbe number and the partial dispersion ratio by containing 5.0% or more. Further, press formability of the glass can be improved. Thus, Nb2O5The content of component (c) is preferably 5.0% as the lower limit, more preferably 6.0% as the lower limit, further preferably 7.0% as the lower limit, further preferably 10.0% as the lower limit, further preferably 13.0% as the lower limit.
On the other hand, by mixing Nb2O5The content of the component (B) is 50.0% or less, so that the material cost of the glass can be reduced. Further, Nb can be reduced while suppressing an increase in melting temperature during glass production2O5Devitrification due to excessive content of the ingredient. Thus, Nb2O5The content of the component (b) is preferably 50.0% or less, more preferably 43.0% or less, still more preferably 40.0% or less, and still more preferably 36.0% or less.
Nb2O5Nb can be used as the component2O5And the like.
The BaO component is an optional component which, when contained in an amount exceeding 0%, can increase the refractive index of the glass, reduce the partial dispersion ratio of the glass, improve the devitrification resistance and the melting property of the glass, and reduce the material cost of the glass as compared with other alkaline earth components such as the CaO component. Further, devitrification and coloration at the time of reheating can be reduced. In particular, the BaO component in the 1 st optical glass is an essential component which can obtain these effects by containing 1.0% or more. Therefore, the content of the BaO component may preferably exceed 0%, more preferably 1.0% as the lower limit, further preferably 2.5% as the lower limit, further preferably 4.5% as the lower limit, further preferably 6.0% as the lower limit, further preferably 10.0% as the lower limit, further preferably 12.0% as the lower limit, further preferably 15.0% as the lower limit.
On the other hand, by setting the content of the BaO component to 50.0% or less, deterioration in resistance to devitrification and chemical durability due to excessive content of the BaO component can be suppressed. Therefore, the content of the BaO component is preferably 50.0% as an upper limit, more preferably 48.0% as an upper limit, and further preferably 45.0% as an upper limit.
BaCO component as a raw material3、Ba(NO3)2And the like.
Li2The O component is an optional component which, when contained in an amount exceeding 0%, can lower the partial dispersion ratio of the glass, can improve the melting property of the glass, and can lower the glass transition temperature. Thus, Li2The content of the O component may be preferably more than 0%, more preferably more than 0.5%, still more preferably more than 1.0%, and still more preferably 1.2% or more.
On the other hand, by mixing Li2The content of the O component is 10.0% or less, and the decrease of the refractive index and the decrease of Li due to the O component can be suppressed2The excessive content of the O component causes creaming and crystal precipitation during the formation of the glass and during reheating, and improves the chemical durability of the glass.
Thus, Li2The content of the O component is preferably 10.0% or less, more preferably 8.0% or less, and further preferably less than 5.0% as an upper limit.
Li2Li as the O component as a raw material2CO3、LiNO3LiF, etc.
The CaO component is an optional component which, when contained in an amount exceeding 0%, can provide an optical glass having a low abbe number and high devitrification resistance and improve the meltability of the glass. Therefore, the content of the CaO component may preferably exceed 0%, more preferably 1.0% as the lower limit, still more preferably 3.5% as the lower limit, and still more preferably 6.7% as the lower limit.
On the other hand, by setting the content of the CaO component to 30.0% or less, it is possible to suppress a decrease in refractive index, an increase in abbe number, and an increase in partial dispersion ratio of the glass, and to suppress deterioration in devitrification resistance of the glass due to excessive content of the CaO component. Further, the material cost of the glass can be reduced, and devitrification and coloring at the time of reheating can be reduced. Therefore, the content of the CaO component is preferably 30.0% as an upper limit, more preferably 25.0% as an upper limit, further preferably 22.0% as an upper limit, further preferably 21.0% as an upper limit, further preferably 20.0% as an upper limit.
CaCO may be used as the CaO component3、CaF2And the like.
The MgO component is an arbitrary component that can lower the melting temperature of the glass by containing more than 0%.
On the other hand, by setting the content of the MgO component to 20.0% or less, it is possible to suppress a decrease in the refractive index of the glass and reduce devitrification of the glass. Further, devitrification and coloration at the time of reheating can be reduced. Therefore, the content of the MgO component is preferably 20.0% or less, more preferably less than 10.0%, even more preferably less than 8.0%, and even more preferably less than 5.0%.
MgO component As raw material, MgO, MgCO3、MgF2And the like.
The SrO component is an arbitrary component that increases the refractive index of the glass and improves resistance to devitrification by containing more than 0%.
In particular, by setting the content of the SrO component to 25.0% or less, deterioration of the chemical durability of the glass can be suppressed. Therefore, the content of the SrO component is preferably 25.0% or less, more preferably 15.0% or less, still more preferably less than 10.0%, still more preferably less than 8.0%, and still more preferably less than 5.0%.
Sr (NO) may be used as the SrO component as a raw material3)2、SrF2And the like.
The total content (mass sum) of the MgO component, CaO component, and SrO component is preferably 30.0% or less. This can reduce devitrification of the glass due to excessive contents of these components and can also improve the chemical durability of the glass. Therefore, the mass sum (MgO + CaO + SrO) is preferably 30.0% or less, more preferably 25.0% or less, still more preferably less than 20.0%, and still more preferably less than 16.0%.
The sum (mass sum) of the contents of RO components (in the formula, R is 1 or more selected from the group consisting of Mg, Ca, Sr, Ba) is preferably 60.0% or less. This can reduce devitrification of the glass due to excessive content of these components. Therefore, the sum of the RO components is preferably 60.0% or less, more preferably 55.0% or less, still more preferably less than 50.0%, and still more preferably less than 48.0% by mass.
On the other hand, the sum of the amounts by mass of the RO components may be preferably more than 0%, more preferably 1.0% or more, still more preferably 5.0% or more, and still more preferably 10.0% or more.
Na2O component and K2The O component is an arbitrary component, and when at least any one of the arbitrary components is contained in excess of 0%, the partial dispersion ratio of the glass can be reduced, the meltability of the glass can be improved, and the glass transition temperature can be lowered.
On the other hand, by adding Na2The content of the O component is 20.0% or less, and the refractive index is less likely to decrease and the chemical durability is less likely to deteriorate. Further, resistance to devitrification at the time of glass formation can be improved, and devitrification and coloring at the time of reheating can be reduced.
Thus, Na2The content of the O component is preferably 20.0% or less, more preferably less than 10.0%, further preferably less than 6.0%, further preferably 3.4% or less, further preferably 2.8% or less.
Furthermore, by mixing K2The content of the O component is 15.0% or less, so that the chemical durability can be made less likely to deteriorate. Further, resistance to devitrification at the time of glass formation can be improved, and devitrification and coloring at the time of reheating can be reduced.
Thus, K2The content of the O component is preferably set to 150% or less, more preferably 10.0% or less, still more preferably 6.0% or less, still more preferably 3.4% or less, and still more preferably 2.0% or less.
Na2O component and K2Na as the O component as a raw material2CO3、NaNO3、NaF、Na2SiF6、K2CO3、KNO3、KF、KHF2、K2SiF6And the like.
Cs2The O component is an arbitrary component that can lower the glass transition temperature by containing more than 0%.
On the other hand, by mixing Cs2The content of O component is 10.0% or less, and Cs content can be reduced2Devitrification of the glass due to excessive content of the O component. Thus, Cs2The content of the O component is preferably 10.0% as an upper limit, more preferably 5.0% as an upper limit, and further preferably 3.0% as an upper limit.
Cs2As the O component, Cs may be used as a raw material2CO3、CsNO3And the like.
Rn2The sum of the mass of the contents of the O components (Rn is 1 or more selected from the group consisting of Li, Na, K, and Cs in the formula) is preferably 20.0% or less. This makes it difficult to reduce the refractive index of the glass and reduces devitrification during glass formation. Thus, Rn2The total content of the O component is preferably 20.0% as an upper limit, more preferably 15.0% as an upper limit, further preferably 11.0% as an upper limit, further preferably 9.0% as an upper limit, further preferably 7.5% as an upper limit, further preferably 5.5% as an upper limit.
ZrO2When the component (b) is an arbitrary component, the refractive index and abbe number of the glass can be increased, the partial dispersion ratio can be reduced, and the devitrification resistance can be improved by containing more than 0% of the arbitrary component. Further, devitrification and coloration at the time of reheating can be reduced. Thus, ZrO2The content of the component (b) may be preferably more than 0%, more preferably 1.0% or more, still more preferably 3.0% or more, and still more preferably more than 4.5%.
On the other hand, by reacting ZrO2The content of the component (b) is 15.0% or less, whereby devitrification of the glass can be reduced and a more homogeneous glass can be easily obtained. Thus, ZrO2The content of component (c) is preferably 15.0% as an upper limit, more preferably 12.0% as an upper limit, and still more preferably 9.0% as an upper limit.
ZrO2ZrO may be used as the component2、ZrF4And the like.
TiO2When the component (b) is an arbitrary component, the refractive index of the glass can be increased and the Abbe number can be decreased to improve resistance to devitrification by containing more than 0%. Thus, TiO2The content of the component (b) is preferably more than 0%, more preferably more than 0.5%, further preferably 1.0% may be a lower limit, and further preferably 1.5% may be a lower limit.
On the other hand, by mixing TiO2The content of the component (A) is 20.0% or less, and the coloring of the glass can be reduced and the internal transmittance of the glass can be improved. In addition, since the partial dispersion ratio is less likely to increase, a desired low partial dispersion ratio close to the reference line can be easily obtained. Thus, TiO2The content of the component (b) is preferably 20.0% as an upper limit, more preferably 17.0% as an upper limit, and further preferably 14.0% as an upper limit.
TiO2Component (C) As a raw material TiO can be used2And the like.
ZrO2Content of component to Nb2O5The ratio of the content of the component (b) is preferably 0.10 to 3.00.
In particular, by setting the ratio to 0.10 or more, the refractive index of the glass can be increased, resistance to devitrification can be improved, the partial dispersion ratio can be reduced, and the material cost of the glass can be reduced. Thus, mass ratio ZrO2/Nb2O5The lower limit is preferably 0.10, more preferably 0.12, still more preferably 0.17, still more preferably 0.23, and yet more preferably 0.25.
On the other hand, by comparing the ratioThe glass devitrification can be reduced by setting the ratio to 3.00 or less. Thus, mass ratio ZrO2/Nb2O5The upper limit is preferably 3.00, more preferably 2.00, still more preferably 1.00, and yet more preferably 0.60.
WO3The component (b) is an optional component which, when contained in an amount exceeding 0%, increases the refractive index of the glass and lowers the abbe number, thereby improving the devitrification resistance of the glass and improving the meltability of the glass.
On the other hand, by mixing WO3The content of the component (b) is 20.0% or less, so that the partial dispersion ratio of the glass is not easily increased, the coloring of the glass is reduced, and the internal transmittance is improved. Thus, WO3The content of component (c) is preferably 20.0% as an upper limit, more preferably 10.0% as an upper limit, further preferably 8.0% as an upper limit, further preferably 5.0% as an upper limit, further preferably 2.5% as an upper limit.
WO3Component (A) As a raw material, WO can be used3And the like.
TiO2Component (B) and Nb2O5Component (B) and WO3The sum (mass sum) of the contents of the components is preferably 10.0% or more and 50.0% or less.
By setting the sum to 10.0% or more, the refractive index of the glass is increased and the devitrification resistance is improved. Thus, mass sum of (TiO)2+Nb2O5+WO3) The lower limit is preferably 10.0%, more preferably 10.0%, still more preferably 15.0%, still more preferably 21.0%, and yet more preferably 25.0%.
On the other hand, by setting the sum to 50.0% or less, an increase in the partial dispersion ratio of the glass can be suppressed. Thus, mass sum of (TiO)2+Nb2O5+WO3) The upper limit is preferably 50.0%, more preferably 48.0%, still more preferably 44.0%, and yet more preferably 40.0%.
B2O3The component (A) is an arbitrary componentWhen the content of the component (b) exceeds 0%, stable glass formation is promoted, and thus devitrification resistance is improved and melting property of the glass is improved. Thus, B2O3The content of the component (b) may preferably exceed 0%, more preferably 1.0% may be the lower limit, still more preferably 1.5% may be the lower limit, and still more preferably 1.8% may be the lower limit.
On the other hand, by mixing B2O3The content of the component is 15.0% or less, thereby suppressing a decrease in refractive index and an increase in the partial dispersion ratio of the glass. Further, devitrification at the time of reheating of the glass can be reduced thereby. Thus, B2O3The content of the component (b) is preferably 15.0% or less, more preferably less than 10.0%, even more preferably less than 5.0%, even more preferably 3.1% or less, even more preferably 2.6% or less.
B2O3Component (C) As a raw material, H3BO3、Na2B4O7、Na2B4O7·10H2O、BPO4And the like.
La2O3Component (b) Gd2O3Component (B) and (Y)2O3Component Yb2O3Ingredient and Lu2O3The component (b) is an arbitrary component, and when at least any one of the arbitrary components is contained in an amount exceeding 0%, the refractive index and abbe number of the glass can be increased and the partial dispersion ratio can be reduced. Wherein, La2O3The content of the component (b) may preferably exceed 0%, more preferably 0.5% as the lower limit, and still more preferably 1.0% as the lower limit.
On the other hand, by mixing La2O3The content of the component (A) is 15.0% or less, so that devitrification of the glass can be reduced, an increase in Abbe number can be suppressed, the specific gravity of the glass can be reduced, and the material cost of the glass can be reduced. Thus, La2O3The content of the component (b) is preferably 15.0% or less, more preferably 12.0% or less, still more preferably less than 10.0%, and still more preferably less than 8.0%.
In addition, Gd is added2O3Component (B) and (Y)2O3Component Yb2O3Ingredient and Lu2O3The content of each component is 10.0% or less, so that devitrification of the glass can be reduced, an increase in abbe number can be suppressed, and the material cost of the glass can be reduced. In particular, by reacting Gd2O3Component Yb2O3Ingredient and Lu2O3The specific gravity of the glass can be reduced by setting the content of each component to 10.0% or less. Thus, Gd2O3Component (B) and (Y)2O3Component Yb2O3Ingredient and Lu2O3The content of each component is preferably 10.0% or less, more preferably less than 8.0%, and still more preferably less than 5.0%.
La2O3Component (b) Gd2O3Component (B) and (Y)2O3Component Yb2O3Ingredient and Lu2O3Component (A) As a raw material La can be used2O3、La(NO3)3·XH2O (X is an arbitrary integer), Y2O3、YF3、Gd2O3、GdF3、Yb2O3、Lu2O3And the like.
Ln2O3The sum (mass sum) of the contents of the components (Ln is 1 or more selected from the group consisting of La, Gd, Y, Yb, Lu in the formula) is preferably 15.0% or less. This can reduce devitrification of the glass, suppress an increase in the abbe number, and reduce the material cost of the glass. Thus, Ln2O3The sum of the mass of the components is preferably 15.0% or less, more preferably 12.0% or less, still more preferably less than 10.0%, and still more preferably less than 8.0%.
B2O3Component (A) and La2O3The total amount (mass sum) of the components is preferably 20.0% or less. This can provide a desired high refractive index and a high transmittance. Therefore, mass and (B)2O3+La2O3) Preferably 20.0% is used asThe upper limit is preferably 15.0%, more preferably 10.0%, and still more preferably 8.5%.
Note that the mass sum (B)2O3+La2O3) From the viewpoint of improving the resistance of the glass to devitrification, it is preferably more than 0%, more preferably more than 0.1%, and still more preferably more than 0.5%.
Al2O3Component (A) and Ga2O3The component (b) is an optional component, and when at least one of the optional components is contained in an amount exceeding 0%, the chemical durability of the glass can be improved and the devitrification resistance of the glass can be improved.
On the other hand, by mixing Al2O3The content of component (A) is 15.0% or less or Ga2O3The content of the component (A) is 10.0% or less, and the content of Al can be reduced2O3Component (C) Ga2O3Devitrification due to excessive content of the ingredient. Further, devitrification and coloration at the time of reheating can be reduced.
Thus, Al2O3The content of the component (b) is preferably 15.0% or less, more preferably less than 10.0%, even more preferably less than 7.0%, even more preferably less than 5.0%.
Furthermore, Ga2O3The content of the component (b) is preferably 10.0% or less, more preferably less than 8.0%, and still more preferably less than 5.0%.
Al2O3Component (A) and Ga2O3Component (C) As a raw material, Al can be used2O3、Al(OH)3、AlF3、Ga2O3、Ga(OH)3And the like.
The ZnO component is an optional component which, when contained in an amount exceeding 0%, can lower the partial dispersion ratio of the glass, improve resistance to devitrification, and lower the glass transition temperature. Therefore, the content of the ZnO component may preferably exceed 0%, more preferably 0.5% as the lower limit, still more preferably 1.0% as the lower limit, and still more preferably 2.0% as the lower limit.
On the other hand, by setting the content of the ZnO component to 10.0% or less, devitrification and coloration at the time of reheating of the glass can be reduced, and the chemical durability of the glass can be improved. Therefore, the content of the ZnO component is preferably 10.0% or less, more preferably less than 8.0%, and still more preferably less than 5.0%.
ZnO or ZnF can be used as the ZnO component2And the like.
GeO2The component (b) is an optional component which, when contained in an amount exceeding 0%, can increase the refractive index of the glass and stabilize the glass to reduce devitrification at the time of molding.
On the other hand, by adding GeO2The content of the component is set to be less than 10.0%, and expensive GeO is reduced2The amount of the components used can reduce the material cost of the glass. Thus, GeO2The content of the component (b) is preferably 10.0% or less, more preferably less than 8.0%, and still more preferably less than 5.0%.
GeO2Ingredient GeO may be used as the raw material2And the like.
P2O5The component (b) is an optional component which improves the stability of the glass by containing more than 0%.
On the other hand, by adding P2O5The content of component (B) is 10.0% or less, and P can be reduced2O5Devitrification due to excessive content of the ingredient. Thus, P2O5The content of the component (b) is preferably 10.0% or less, more preferably less than 8.0%, and still more preferably less than 5.0%.
P2O5Component (C) As a raw material, Al (PO) can be used3)3、Ca(PO3)2、Ba(PO3)2、BPO4、H3PO4And the like.
Ta2O5When the component (b) is an arbitrary component, the refractive index of the glass can be increased, the abbe number and the partial dispersion ratio of the glass can be decreased, and the devitrification resistance of the glass can be improved by containing the arbitrary component in excess of 0%.
On the other hand, by mixing Ta2O5The content of the component (A) is 10.0% or less, thereby reducing Ta which is a rare mineral resource2O5The amount of the component(s) used and the glass is easily melted at a lower temperature, so that the production cost of the glass can be reduced. Furthermore, Ta can be reduced thereby2O5Devitrification of the glass due to excessive content of the components. Thus, Ta2O5The content of the component (b) is preferably 10.0% or less, more preferably 8.0% or less, and further preferably 5.0% or less. In particular, Ta may not be contained from the viewpoint of reducing the material cost of glass2O5And (3) components.
Ta2O5Ta as the component (A) may be used2O5And the like.
Bi2O3The component (b) is an arbitrary component which can increase the refractive index of the glass, decrease the abbe number and lower the glass transition temperature by containing more than 0%.
On the other hand, by adding Bi2O3The content of the component (A) is 10.0% or less, so that the partial dispersion ratio of the glass is not easily increased, and the coloring of the glass can be reduced to improve the internal transmittance. Thus, Bi2O3The content of the component (b) is preferably 10.0% or less, more preferably less than 8.0%, and still more preferably less than 5.0%.
Bi2O3Component (B) As a raw material Bi can be used2O3And the like.
TeO2The component (b) is an arbitrary component which can increase the refractive index of the glass, decrease the partial dispersion ratio of the glass, and lower the glass transition temperature when the arbitrary component is contained in an amount exceeding 0%.
On the other hand, by mixing TeO2When the content of the component (B) is 10.0% or less, the coloring of the glass can be reduced and the internal transmittance can be improved. In addition, by reducing the expensive TeO2The amount of the component (a) used makes it possible to obtain glass with a lower material cost. Thus, TeO2The content of the component (A) is preferably 10.0% or less,More preferably, it is less than 8.0%, and still more preferably, it is less than 5.0%.
TeO2Component (A) TeO can be used as a raw material2And the like.
Sb2O3The component (b) is an optional component which can promote the deaeration of the glass and clarify the glass when the optional component is contained in an amount exceeding 0%.
On the other hand, by mixing Sb2O3The content of the component (C) is 1.0% or less, so that excessive foaming at the time of melting glass is less likely to occur, and Sb can be made to be Sb2O3The components are not easy to alloy with melting equipment (particularly noble metals such as Pt). Thus, Sb2O3The content of component (b) is preferably 1.0% as the upper limit, more preferably 0.5% as the upper limit, and still more preferably 0.1% as the upper limit. When importance is attached to the environmental impact of the optical glass, Sb may not be contained2O3And (3) components.
Sb2O3Component (C) Sb as a raw material2O3、Sb2O5、Na2H2Sb2O7·5H2O, and the like.
The components for refining and degassing glass are not limited to Sb described above2O3As the component (b), a refining agent, a defoaming agent, or a combination thereof, which is known in the field of glass production, can be used.
< ingredients not to be contained >
Next, components that should not be contained in the optical glass of the present invention and components that are not preferably contained therein will be described.
Other components may be added as needed within a range not impairing the characteristics of the glass of the invention of the present application. In particular, it is preferable that the optical glass substantially not contain transition metal components other than Ti, Zr, Nb, W, La, Gd, Y, Yb, and Lu, such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo, because the glass is colored and absorbs at a specific wavelength in the visible light region even when the glass contains a small amount of each of the transition metal components alone or in combination.
Further, lead compounds such As PbO and As2O3The arsenic compound is a component having a high environmental load, and therefore, it is desirable that the arsenic compound is not substantially contained, that is, is never contained except for unavoidable contamination.
Further, each component of Th, Cd, Tl, Os, Be, and Se tends to Be used as a harmful chemical material in recent years, and measures against the environment are required not only in the glass production process but also in the processing process and the treatment after commercialization. Therefore, when the environmental influence is considered important, it is preferable that these elements are not substantially contained.
The composition of the glass composition of the present invention is expressed in terms of mass% of the total mass of the glass relative to the composition in terms of oxides, and therefore is not directly expressed in terms of mol%, and the composition in terms of mol% of each component present in the glass composition satisfying each required characteristic in the present invention is approximately the following value in terms of composition in terms of oxides.
SiO2The component(s) are 15.0 to 60.0 mol% and
Nb2O5the components are 3.0-30.0 mol%
And
Cathe content of the O component is0 to 45.0 mol%
BaThe content of the O component is0 to 20.0 mol%
Li2The content of the O component is0 to 30.0 mol%
MgO ingredient is0 to 40.0 mol%
The SrO content is 0-20.0 mol%
Na2The content of the O component is0 to 35.0 mol%
K2The content of the O component is0 to 20.0 mol%
Cs2The content of the O component is0 to 10.0 mol%
ZrO2The components are 0 to 15.0 mol%
TiO2The components are 0 to 20.0 mol%
WO3Comprises the following components0 to 20.0 mol%
B2O3The components are 0 to 20.0 mol%
La2O3The components are 0 to 10.0 mol%
Gd2O3The components are 0 to 8.0 mol percent
Y2O3The components are 0 to 10.0 mol%
Yb2O3The components are 0 to 8.0 mol percent
Lu2O3The components are 0 to 8.0 mol percent
Al2O3The components are 0 to 15.0 mol%
ZnO content of 0 to 15.0 mol%
GeO2The components are 0 to 10.0 mol%
Ga2O3The components are 0 to 8.0 mol percent
P2O5The components are 0 to 20.0 mol%
Ta2O5The components are 0 to 8.0 mol percent
Bi2O3The components are 0 to 5.0 mol percent
TeO2The components are 0 to 10.0 mol%
Sb2O3The components are 0 to 1.0 mol%
In particular, the content of the BaO component in mol% in the 1 st optical glass is a value of approximately 1.0 to 20.0 mol%.
[ production method ]
The optical glass of the present invention is produced, for example, as follows. That is, the raw materials are uniformly mixed so that each component is within a predetermined content range, the prepared mixture is put into a platinum crucible, a quartz crucible, or an alumina crucible to be roughly melted, then put into a gold crucible, a platinum alloy crucible, or an iridium crucible, melted at a temperature of 1100 to 1400 ℃ for 3 to 5 hours, stirred, homogenized, defoamed, etc., then cooled to a temperature of 1000 to 1400 ℃, finally stirred to remove streaks/textures, poured into a mold, and slowly cooled to prepare the alloy.
< Properties >
The optical glass of the present invention preferably has a high refractive index and an abbe number within a predetermined range.
The refractive index (nd) of the optical glass of the present invention is preferably 1.70 as the lower limit, more preferably 1.75 as the lower limit, further preferably 1.80 as the lower limit, and further preferably 1.82 as the lower limit. The upper limit of the refractive index may be preferably 1.95 or less, more preferably 1.90 or less, still more preferably 1.88 or less, and still more preferably 1.86 or less.
The abbe number (ν d) of the optical glass of the present invention is preferably 35 as an upper limit, more preferably 33 as an upper limit, and further preferably 32 as an upper limit. On the other hand, the abbe number (ν d) of the optical glass of the present invention is preferably 25 or more, more preferably more than 27, and still more preferably more than 29.
The optical glass of the present invention having such a refractive index and abbe number is useful in optical design, and can realize particularly high imaging characteristics and the like and also realize miniaturization of an optical system, so that the degree of freedom in optical design can be increased.
The optical glass of the present invention has a low partial dispersion ratio (θ g, F).
More specifically, the optical glass of the present invention satisfies the relationship of (-0.00162X v d +0.63622) ≦ theta g, F) ≦ 0.00275X v d +0.68125 in the range of vd ≦ 31 and the relationship of (-0.00162X v d +0.63622) ≦ theta g, F) ≦ 0.00162X v d +0.64622 in the range of vd >31 between the partial dispersion ratio (theta g, F) and the Abbe number (vd ≦ 31). Thus, since an optical glass having a partial dispersion ratio (θ g, F) close to the reference line can be obtained, chromatic aberration of an optical element formed of the optical glass can be reduced.
The lower limit of the partial dispersion ratio (. theta.g, F) of vd. ltoreq.31 is preferably (-0.00162X vd +0.63622), more preferably (-0.00162X vd +0.63822), further preferably (-0.00162X vd +0.63922), and further preferably (-0.00162X vd + 0.64022).
The upper limit of the partial dispersion ratio (. theta.g, F) of ν d.ltoreq.31 is preferably (-0.00275 × ν d +0.68125), more preferably (-0.00275 × ν d +0.68025), further preferably (-0.00275 × ν d +0.67925), further preferably (-0.00275 × ν d +0.67900), and further preferably (-0.00275 × ν d + 0.67895).
The lower limit of the partial dispersion ratio (θ g, F) of vd >31 is preferably (-0.00162 × vd +0.63622), more preferably (-0.00162 × vd +0.63822), still more preferably (-0.00162 × vd +0.63922), and still more preferably (-0.00162 × vd + 0.64022).
The upper limit of the partial dispersion ratio (θ g, F) of vd >31 is preferably (-0.00162 × vd +0.64622), more preferably (-0.00162 × vd +0.64522), still more preferably (-0.00162 × vd +0.64422), still more preferably (-0.00162 × vd +0.64397), and still more preferably (-0.00162 × vd + 0.64392).
In particular, in a region where the abbe number (ν d) is small, the partial dispersion ratio (θ g, F) of a general glass is higher than the reference line, and the relationship between the partial dispersion ratio (θ g, F) and the abbe number (ν d) of a general glass is represented by a curve. However, since it is difficult to approximate the curve, in the present invention, a straight line having a different slope with ν d ═ 31 as a boundary is used to indicate that the partial dispersion ratio (θ g, F) is low as compared with general glass.
The optical glass of the present invention is preferably less colored. In particular, when the optical glass of the present invention is expressed by the transmittance of glass, a sample having a thickness of 10mm shows a wavelength (. lamda.) of 70% of the spectral transmittance70) Preferably 450nm or less, more preferably 430nm or less, and still more preferably 420nm or less. Further, a sample of the optical glass of the present invention having a thickness of 10mm shows a wavelength (. lamda.) of a spectral transmittance of 5%5) Preferably 400nm or less, more preferably 380nm or less, and still more preferably 360nm or less. This makes it possible to improve the transparency of the glass in the visible light region because the absorption edge of the glass is located in the vicinity of the ultraviolet region, and therefore the optical glass can be preferably used as a material for an optical element such as a lens.
The optical glass of the present invention is preferably small in specific gravity. More specifically, the specific gravity of the optical glass of the present invention is preferably 5.50[ g/cm [ ]3]The following. This reduces the quality of the optical element and the optical instrument using the same, and thus can contribute to the optical instrumentThe weight is reduced. Therefore, the specific gravity of the optical glass of the present invention is preferably 5.50 as an upper limit, more preferably 5.40 as an upper limit, and further preferably 5.30 as an upper limit. The optical glass of the present invention has a specific gravity of at most approximately 3.00 or more, more specifically 3.50 or more, and still more specifically 4.00 or more.
The specific gravity of the optical glass of the present invention is measured based on "method for measuring specific gravity of optical glass" of Japanese society for optical and glass industries, Standard JOGIS 05-1975.
The optical glass of the present invention preferably has high devitrification resistance (in the specification, it may be referred to simply as "devitrification resistance") when it is produced. This makes it possible to suppress a decrease in transmittance due to crystallization of the glass during glass production, and therefore the optical glass can be preferably used for an optical element that transmits visible light, such as a lens. As a scale showing high devitrification resistance in glass production, for example, a case where the liquid phase temperature is low is cited.
The optical glass of the present invention is preferably excellent in press formability. That is, the optical glass of the present invention preferably does not cause devitrification or opalescence even before and after the reheating test (1). This makes it possible to easily perform reheating treatment such as reheat pressing on glass, since devitrification and coloration are less likely to occur even in a reheat test in which reheat pressing is expected, and the light transmittance of glass is less likely to be lost. That is, since the optical element having a complicated shape can be manufactured by press molding, the optical element can be manufactured at low manufacturing cost with high productivity.
The reheating test (1) can be carried out by placing a test piece of 15mm × 15mm × 30mm on a concave refractory, putting the test piece on an electric furnace, reheating the test piece, raising the temperature from room temperature to a temperature 80 to 150 ℃ higher than the transition temperature (Tg) of each sample (falling temperature of the refractory) after 150 minutes, holding the temperature at the temperature for 30 minutes, cooling the test piece to room temperature, taking the test piece out of the furnace, polishing the opposite 2 surfaces to a thickness of 10mm to allow observation from the inside, and then visually observing the polished glass sample.
The "absence or presence of devitrification and opalescence before and after the reheating test (1)" means that, for example, the transmittance of light (d-ray) having a wavelength of 587.56nm of the test piece after the reheating test (1) divided by the transmittance of d-ray of the test piece before the reheating test is substantially 0.80 or more.
[ preform and optical element ]
The glass molded body can be produced from the produced optical glass by a press molding method such as reheat press molding and precision press molding. That is, a preform for press molding may be prepared from an optical glass, the preform may be subjected to reheat press molding and then to polishing to prepare a glass molded body, or the preform subjected to polishing may be subjected to precision press molding to prepare a glass molded body. The method for producing the glass molded product is not limited to these methods.
The glass molded article produced in this way is useful for various optical elements, and is particularly preferably used for optical elements such as lenses and prisms. This can reduce color bleeding due to chromatic aberration in transmitted light of an optical system provided with the optical element. Therefore, when the optical element is used in a camera, an object to be photographed can be expressed more accurately, and when the optical element is used in a projector, a desired image can be projected with higher definition.
Examples
Tables 1 to 14 show the compositions of examples (nos. 1 to 101) and comparative example (No. a) of the present invention, and the wavelengths (λ g, F) at which the refractive index (nd), the abbe number (ν d), the partial dispersion ratio (θ g, F) and the spectral transmittances are 5% and 70%5、λ70) Specific gravity and results of the reheating test (bath sinking test). The following examples are given for illustrative purposes only and are not intended to be limiting.
The glasses of the examples and comparative examples of the present invention were all produced as follows: high-purity raw materials generally used for optical glass, such as oxides, hydroxides, carbonates, nitrates, fluorides, hydroxides, metaphosphoric acid compounds, which are equivalent to the raw materials of the respective components, are selected, weighed and uniformly mixed so as to achieve the composition ratios of the respective examples and comparative examples shown in the table, and then put into a platinum crucible, melted in an electric furnace at a temperature range of 1100 to 1400 ℃ for 3 to 5 hours depending on the melting difficulty of the glass composition, homogenized by stirring, defoamed, and the like, and then, the temperature is reduced to 1000 to 1400 ℃, homogenized by stirring, poured into a mold, and slowly cooled to produce glass.
Here, the refractive index (nd), abbe number (ν d), and partial dispersion ratio (θ g, F) of the glasses of examples and comparative examples were measured based on japanese optical glass society standard JOGIS 01-2003. Then, for the values of the abbe number (ν d) and the partial dispersion ratio (θ g, F) obtained, an intercept b is obtained when the slope a is 0.00162 and 0.00275 in the relational expression (θ g, F) — a × ν d + b. The glass used in the present measurement was treated in an annealing furnace at an annealing temperature reduction rate of-25 ℃/hr.
The transmittance of the glasses of examples and comparative examples was measured based on the japanese optical glass agency standard JOGIS 02. In the present invention, the presence or absence of coloring and the degree of coloring of glass are determined by measuring the transmittance of glass. Specifically, the spectral transmittance at 200 to 800nm was measured for a parallel-polished surface having a thickness of 10. + -. 0.1mm by JIS Z8722 to determine λ5(wavelength at 5% transmittance) and lambda70(wavelength at a transmittance of 70%).
The specific gravities of the glasses of examples and comparative examples were measured based on "method for measuring specific gravity of optical glass" of Japanese society for optical and glass industries, JOGIS 05-1975.
Further, with respect to the glasses of examples and comparative examples, the presence or absence of devitrification and opalescence before and after the reheating test were visually confirmed. Here, devitrification and opalescence before and after the reheat test were confirmed as follows: a test piece of 15mm by 30mm was placed on a concave refractory, put into an electric furnace, reheated to a reheating temperature, kept at the temperature for 30 minutes, cooled to a normal temperature, taken out of the furnace, and the opposite 2 surfaces were polished to a thickness of 10mm so as to be observable from the inside, and then the presence or absence of devitrification and opalescence of the polished glass sample were visually observed. In this case, the glass which did not cause devitrification or opalescence when the reheating temperature was set to (Tg +80 ℃ C. -150 ℃ C.) and did not cause devitrification or opalescence when the reheating temperature was set to a temperature higher than (Tg +80 ℃ C. -150 ℃ C.), the "cell sinking test (model No. し) (test)" was described as "O". Further, the "bath deposition test" is described as "Δ" for a glass in which devitrification and opalescence are not generated when the reheating temperature is a specific temperature in the range of (Tg +80 ℃ to 150 ℃), but devitrification and opalescence are generated when the reheating temperature is a temperature higher than the range of (Tg +80 ℃ to 150 ℃). Further, the "tank sinking test" is indicated as "X" for a glass which generates devitrification or opalescence when the reheating temperature is set to a specific temperature in the range of (Tg +80 ℃ C. to 150 ℃ C.).
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
TABLE 6
TABLE 7
TABLE 8
TABLE 9
TABLE 11
TABLE 12
Watch 13
TABLE 14
With respect to the optical glass of the examples of the present invention, the partial dispersion ratio (θ g, F) of the glass having vd. ltoreq.31 is (-0.00275X vd +0.68125) or less. In addition, for the glass with vd >31, the partial dispersion ratio (θ g, F) is (-0.00162 × vd +0.64622) or less. On the other hand, the optical glass of the examples of the present invention had a partial dispersion ratio (θ g, F) of (-0.00162 × ν d +0.63622) or more. That is, the relationship between the partial dispersion ratio (θ g, F) and the abbe number (ν d) of the glasses of examples of the present application is shown in fig. 2. Therefore, it is found that their partial dispersion ratios (θ g, F) are within a desired range.
On the other hand, the glasses of comparative examples (No. A) of the present invention each had vd not more than 31 and a partial dispersion ratio (θ g, F) exceeding (-0.00275 × vd + 0.68125). Therefore, it is clear that the optical glass of the example of the present invention has a smaller partial dispersion ratio (θ g, F) in the relational expression with the abbe number (ν d) than the glass of the comparative example.
In addition, the refractive index (nd) of the optical glass of the examples of the present invention is 1.70 or more, more specifically 1.83 or more and 1.95 or less, more specifically 1.87 or less, within a desired range.
The abbe number (ν d) of the optical glass according to the example of the present invention is 25 or more, more specifically 28 or more, and 35 or less, more specifically 32 or less, each within a desired range.
Further, λ of the optical glass of the embodiment of the present invention70(wavelength at a transmittance of 70%) is 450nm or less, more specifically 430nm or less. Further, λ of the optical glass of the embodiment of the present invention5(wavelength at 5% transmittance) is 400nm or less, more specifically 360nm or less. Therefore, it is clear that the optical glass of the examples of the present invention has high transmittance for visible light and is difficult to be colored.
Therefore, it is understood from the optical glasses of the examples that the optical glasses have desired refractive index (nd) and abbe number (vd), high transmittance for visible light, and small chromatic aberration.
The specific gravities of the optical glasses of the examples are 5.00 or less, more specifically 4.50 or less, within desired ranges.
Further, the optical glasses of the examples were less likely to cause devitrification and opalescence before and after the reheating test (1). Therefore, it is assumed that the optical glass according to the example of the present invention is less likely to cause devitrification or milky white by reheating, and has high press formability.
Further, by using the optical glass of the example, a lens preform was formed, and press molding was performed on the lens preform, and as a result, various lens shapes could be stably processed.
It is understood that the present invention has been described in detail for the purpose of illustration and that the present embodiments are illustrative only and that many changes and modifications can be made by one skilled in the art without departing from the spirit and scope of the invention.
Claims (16)
1. An optical glass containing 10.0 to 30.0 mass% of SiO25.0% or more and less than 36.0% of Nb2O5Component (B), a BaO component of 20.014-50.0%, and La2O3The content of component B is less than 10.0%2O3The content of the component (A) is less than 10.0%, the content of the ZnO component (A) is less than 8.0%, and the sum of the masses of the RO components is 30.421% or more and 60.0% or less, wherein R is 1 or more selected from the group consisting of Mg, Ca, Sr and Ba, Rn2The sum of the O components is 9.0% or less by mass, and Rn is represented by the formula2In O, Rn is more than 1 selected from the group consisting of Li, Na, K and Cs, TiO2+Nb2O5+WO3The mass sum of (a) is 25.751% or more and 50.0% or less, has a refractive index (nd) of 1.80 or more and 1.95 or less, has an Abbe's number (vd) of 25 or more and 35 or less, satisfies a relation of (-0.00162 x vd +0.63622) or less (theta g, F) or less (-0.00275 x vd +0.68125) in the range of vd or less from vd to 31 between a partial dispersion ratio (theta g, F) and the Abbe's number (vd)>The range of 31 satisfies the relation of (-0.00162 x ν d +0.63622) ≦ (θ g, F) ≦ (0.00162 x ν d + 0.64622).
2. The optical glass according to claim 1, wherein Li is in mass%2The content of the O component is 8.0% or less.
3. The optical glass according to claim 1, wherein the content of the CaO component is 30.0% by mass or less.
4. The optical glass according to claim 1, wherein the glass composition is, in mass%,
0 to 20.0% of MgO component,
The SrO content is 0-25.0%.
5. The optical glass according to claim 1, wherein the sum by mass of MgO + CaO + SrO is 30.0% or less.
6. The optical glass according to claim 1, wherein the glass composition is, in mass%,
Na20 to less than 6.0 percent of O component,
K2The O component is0 to less than 6.0 percent.
7. The optical glass according to claim 1, wherein ZrO is contained in an amount of 1.0% by mass or more and 15.0% by mass or less2Component (C), more than 0% and 20.0% or less of TiO2And (3) components.
8. The optical glass according to claim 1, wherein ZrO is present in a mass ratio2/Nb2O5Is 0.10 to 3.00 inclusive.
9. The optical glass according to claim 1, wherein WO is in mass%3The content of the component is 20.0% or less.
10. The optical glass according to claim 1, wherein the glass composition is, in mass%,
Gd2O30 to 10.0 percent of components,
Y2O30 to 10.0 percent of components,
Yb2O30 to 10.0 percent of components,
Lu2O3The content of the components is 0-10.0%.
11. The optical glass according to claim 1, wherein B is2O3+La2O3The sum of the mass of (a) is 15.0% or less.
12. The optical glass according to claim 1, wherein the glass composition is, in mass%,
Al2O30 to 15.0 percent of components,
GeO20 to 10.0 percent of components,
Ga2O30 to 10.0 percent of components,
P2O50 to 10.0 percent of components,
Ta2O50 to 10.0 percent of components,
Bi2O30 to 10.0 percent of components,
TeO20 to 10.0 percent of components,
Sb2O3The component is 0-1.0%.
13. The optical glass according to claim 1, wherein the spectral transmittance shows a wavelength (λ) of 70%70) Is 450nm or less.
14. A preform for polishing and/or precision press molding, which is formed from the optical glass according to any one of claims 1 to 13.
15. An optical element obtained by grinding and/or polishing the optical glass according to any one of claims 1 to 13.
16. An optical element produced by precision press molding the optical glass according to any one of claims 1 to 13.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2013095764 | 2013-04-30 | ||
| JP2013095763 | 2013-04-30 | ||
| JP2013-095763 | 2013-04-30 | ||
| JP2013-095764 | 2013-04-30 | ||
| JP2014-056905 | 2014-03-19 | ||
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| JP2014056906 | 2014-03-19 | ||
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| JP6932423B2 (en) * | 2015-11-06 | 2021-09-08 | 株式会社オハラ | Optical glass, preforms and optics |
| CN106927674A (en) * | 2015-11-11 | 2017-07-07 | 株式会社小原 | A kind of optical glass, prefabricated component and optical element |
| US10370289B2 (en) | 2015-11-11 | 2019-08-06 | Ohara Inc. | Optical glass, preform, and optical element |
| CN118221347A (en) * | 2015-12-07 | 2024-06-21 | 株式会社小原 | Optical glass, prefabricated member and optical element |
| CN106915901A (en) * | 2015-12-25 | 2017-07-04 | 株式会社小原 | A kind of optical glass, prefabricated component and optical element |
| CN107445475B (en) * | 2016-06-24 | 2020-02-07 | 成都光明光电股份有限公司 | Optical glass, optical preform and optical element |
| CN109592898B (en) * | 2017-10-02 | 2023-09-19 | 株式会社小原 | Optical glass, preform and optical element |
| CN107963808B (en) * | 2017-12-13 | 2022-01-25 | 成都光明光电股份有限公司 | Glass composition and chemically tempered glass |
| CN108249755A (en) * | 2018-03-27 | 2018-07-06 | 成都光明光电股份有限公司 | Optical glass |
| US11667561B2 (en) * | 2018-11-26 | 2023-06-06 | Corning Incorporated | Glass material with a high index of refraction |
| CN110482854A (en) * | 2019-09-30 | 2019-11-22 | 成都光明光电股份有限公司 | Optical glass, its manufactured optical precast product, optical element and optical instrument |
| CN115028353B (en) * | 2022-06-22 | 2023-08-08 | 成都光明光电有限责任公司 | Optical glass with negative anomalous dispersion |
| CN115448591B (en) * | 2022-10-18 | 2023-07-25 | 成都光明光电股份有限公司 | Optical glass, optical element and optical instrument |
| CN115466049B (en) * | 2022-10-18 | 2023-08-08 | 成都光明光电股份有限公司 | Optical glass |
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| JP5727689B2 (en) * | 2008-03-31 | 2015-06-03 | 株式会社オハラ | Optical glass, optical element and optical instrument |
| JP2010105902A (en) * | 2008-09-30 | 2010-05-13 | Ohara Inc | Optical glass and method for suppressing deterioration of spectral transmittance |
| JP2011037660A (en) * | 2009-08-07 | 2011-02-24 | Ohara Inc | Optical glass, lens preform and optical element |
| JP6014301B2 (en) * | 2010-06-24 | 2016-10-25 | 株式会社オハラ | Optical glass, preform and optical element |
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