JP5689736B2 - Optical glass, optical element and preform - Google Patents

Description

  The present invention relates to an optical glass, an optical element, and a preform.

  A lens system of an optical apparatus is usually designed by combining a plurality of glass lenses having different optical properties. In recent years, characteristics required for lens systems of optical devices have been diversified, and optical glasses having optical characteristics that have not been noticed in the past have been developed in order to further increase the degree of freedom of design. Among them, optical glass characterized by anomalous dispersion (Δθg, F) has been attracting attention as having a remarkable effect on aberration color correction.

For example, in Patent Documents 1 to 3, in addition to the properties of high refractive index and low dispersibility, which are conventionally required, and excellent workability, as an optical glass having high anomalous dispersion, for example, P ⁵⁺ , Al ³ as a cation component. There has been proposed an optical glass containing ⁺ , alkaline earth metal ions and the like, and containing F ⁻ and O ²⁻ as anionic components.

JP 2007-55883 A JP 2008-137877 A International Publication No. 2008/111439 Pamphlet

  However, the conventional optical glasses as described in Patent Documents 1 to 3 have an insufficient degree of anomalous dispersion, and development of optical glasses having higher anomalous dispersion is desired.

The present invention aims to solve such problems.
That is, the object of the present invention is that the chromatic aberration of the glass lens can be corrected with high accuracy due to higher anomalous dispersion, and further, it has a high refractive index and low dispersion, and in addition, has excellent devitrification resistance. It is to provide an optical glass, an optical element and a preform.

The present inventors have intensively studied to solve the above problems, and have completed the present invention.
The present invention includes the following (1) to (7).
(1) P ⁵⁺ , Al ³⁺ and R ²⁺ (R ²⁺ is at least one selected from the group consisting of Mg ²⁺ , Ca ²⁺ , Sr ²⁺ and Ba ²⁺ ) as a cation component. Including
In terms of cation%, the Ca ²⁺ content is 14.0 to 24.0%, the R ²⁺ content is 32.0 to 58.0%,
As an anion component, F ^- containing and O ^2-,
An optical glass having a refractive index (nd) of 1.50 or more and an Abbe number (νd) of 65 or more.
(2) The optical glass according to (1), wherein the content of F ⁻ is 20.0 to 95.0% in terms of anion%.
(3) As a cation component, further contains Ln ³⁺ (Ln ³⁺ is at least one selected from the group consisting of Y ³⁺ , La ³⁺ , Gd ³⁺ , Yb ³⁺ and Lu ³⁺ ). ,
The optical glass according to (1) or (2), wherein the total content of Ln ³⁺ is 0 to 10.0% in terms of cation%.
(4) An optical element comprising the optical glass according to any one of (1) to (3) above.
(5) A preform for polishing and / or precision press molding comprising the optical glass according to any one of (1) to (3) above.
(6) An optical element obtained by polishing the preform described in (5).
(7) An optical element obtained by precision pressing the preform described in (5).

  According to the present invention, optical glass that can correct chromatic aberration of a glass lens with high accuracy due to higher anomalous dispersion, has a high refractive index and low dispersion, and is excellent in devitrification resistance. Optical elements and preforms can be provided.

It is a figure which shows the normal line by which partial dispersion ratio ((theta) g, F) is represented on the orthogonal coordinate of a vertical axis | shaft, and Abbe number ((nu) d) on a horizontal axis.

The present invention will be described.
In the present invention, P ⁵⁺ , Al ³⁺ and R ²⁺ (R ²⁺ is at least one selected from the group consisting of Mg ²⁺ , Ca ²⁺ , Sr ²⁺ and Ba ²⁺ ) as the cation component. include, by cationic%, the content of Ca ²⁺ is from 14.0 to 24.0%, content of R ²⁺ is from 32.0 to 58.0%, as an anionic component, F ^- and O ^2- is an optical glass having a refractive index (nd) of 1.50 or more and an Abbe number (νd) of 65 or more.
Hereinafter, such an optical glass is also referred to as “optical glass of the present invention”.

One feature of the optical glass of the present invention is that it contains a specific amount of R ²⁺ and a specific amount of Ca ²⁺ belonging to R ²⁺ .
The inventor contains P ⁵⁺ and Al ³⁺ , contains a specific amount of each of R ²⁺ and Ca ²⁺ , contains F ⁻ and O ²⁻ (preferably a specific amount), has a refractive index and Optical glass with an Abbe number greater than a specific value has a higher anomalous dispersion (Δθg, F) than conventional ones, and can correct chromatic aberration of the glass lens with high accuracy, with a high refractive index and low dispersion. In addition, the present inventors have found that the devitrification resistance is excellent and completed the present invention.

<Glass component>
Each component which comprises the optical glass of this invention is demonstrated.
In the present specification, unless otherwise specified, the content of each component is expressed in terms of cation% or anion% based on the molar ratio. Here, “cation%” and “anion%” are contained in the glass by separating the glass component of the optical glass of the present invention into a cation component and an anion component, and the total ratio is 100 mol% in each. It is the composition which described each component.

[Cation component]
<P ⁵⁺ >
The optical glass of the present invention contains P ⁵⁺ . P ⁵⁺ is a glass-forming component and has properties of suppressing devitrification, increasing the refractive index, and suppressing the Abbe number from decreasing.
Since such properties are strengthened, the P ⁵⁺ content is preferably 22.0 to 55.0%. The content of P ⁵⁺ is preferably 24.0%, more preferably 26.0%, more preferably 27.0%, still more preferably 28.0%, preferably 52.0%, more The upper limit is preferably 50.0%, more preferably 49.0%, and still more preferably 48.0%.
P ⁵⁺ is contained in the glass using, for example, Al (PO ₃ ) ₃ , Ca (PO ₃ ) ₂ , Ba (PO ₃ ) ₂ , Zn (PO ₃ ) ₂ , BPO ₄ , H ₃ PO _4, etc. as raw materials. It can be included.

<Al ³⁺ >
The optical glass of the present invention contains Al ³⁺ . Al ³⁺ has the properties of increasing the devitrification resistance, refractive index and Abbe number of the glass, lowering the degree of wear, and further improving the workability.
Since such properties are strengthened, the content of Al ³⁺ is preferably 3.0 to 15.0%. The content of Al ³⁺ is preferably 4.0%, more preferably 5.0%, still more preferably 6.0%, preferably 13.0%, more preferably 11.0%, Preferably, the upper limit is 10.0%.
Al ³⁺ can be contained in the glass using, for example, Al (PO ₃ ) ₃ , AlF ₃ , Al ₂ O ₃ or the like as a raw material.

<R2 ⁺ >
The optical glass of the present invention contains 32.0 to 58.0% of R ²⁺ . R ²⁺ means at least one selected from the group consisting of Mg ²⁺ , Ca ²⁺ , Sr ²⁺ and Ba ²⁺ . The content of R ²⁺ means the total content of these four ions. As will be described later, the optical glass of the present invention always contains Ca ²⁺ out of R ²⁺ .
When R ²⁺ is in such a range and Ca ²⁺ is in a specific range described later, the anomalous dispersion (Δθg, F) is high and the chromatic aberration of the glass lens is highly accurate compared to the conventional one. An optical glass that can be corrected, has a high refractive index and low dispersibility, and has excellent devitrification resistance can be obtained. Further, a stable glass can be obtained when the content of R ²⁺ is in such a range.
The content of R ²⁺ is more preferably 34.0%, more preferably 35.0%, more preferably 36.0%, more preferably 37.0%, and still more preferably 38.0%. More preferably, the upper limit is 57.5%, more preferably 57.0%, more preferably 56.5%, and still more preferably 56.0%.

<Ca ²⁺ >
The optical glass of the present invention contains 14.0 to 24.0% Ca ²⁺ . When the Ca ²⁺ content is in such a range and the R ²⁺ content is in the specific range as described above, the anomalous dispersion (Δθg, F) is higher than that of the conventional glass. It is possible to correct the chromatic aberration of the lens with high accuracy, and to obtain an optical glass having a high refractive index and a low dispersibility and having excellent devitrification resistance.
Since such properties are strengthened, the Ca ²⁺ content is more preferably 14.5%, more preferably 15.0%, still more preferably 16.0%, and more preferably 23.5%. More preferably, the upper limit is 23.0%, more preferably 22.0%, and still more preferably 21.0%.
Ca ²⁺ can be contained in the glass using, for example, Ca (PO ₃ ) ₂ , CaCO ₃ , CaF ₂ or the like as a raw material.

<Mg ²⁺ >
The optical glass of the present invention may contain Mg ²⁺ as one of R ²⁺ . Mg ²⁺ has the property of increasing the devitrification resistance of the glass and lowering the degree of wear.
Since such properties are strengthened, the Mg ²⁺ content is preferably 1.0 to 20.0%. The Mg ²⁺ content is more preferably 3.0%, still more preferably 5.0%, more preferably 17.0%, more preferably 15.0%, more preferably 12.0%. More preferably, the upper limit is 10.0%, and even more preferably 9.0%.
Mg ²⁺ can be contained in the glass using, for example, MgO, MgF ₂ or the like as a raw material.

<Ba ²⁺ >
The optical glass of the present invention may contain Ba ²⁺ as one of R ²⁺ . Ba ²⁺ increases the stability of the glass. Moreover, it has the property of maintaining low dispersibility and increasing the refractive index.
Since such properties are strengthened, the Ba ²⁺ content is preferably 0% to 40.0%. The Ba ²⁺ content is more preferably 2.0%, more preferably 3.0%, more preferably 10.0%, more preferably 15.0%, more preferably 17.0%. 35.0%, more preferably 32.0%, more preferably 30.0%, more preferably 29.0%, more preferably 20.0%, more preferably 19.0%, The upper limit is preferably 18.0.
Ba ²⁺ can be contained in the glass by using, for example, Ba (PO ₃ ) ₂ , BaCO ₃ , Ba (NO ₃ ) ₂ , BaF ₂ or the like as a raw material.

<Sr ²⁺ >
The optical glass of the present invention may contain Sr ²⁺ as one of R ²⁺ . Sr ²⁺ has the property of increasing the devitrification resistance of the glass and suppressing the decrease in the refractive index.
Since such properties are strengthened, the Sr ²⁺ content is preferably 0% to 20.0%. The Sr ²⁺ content is more preferably 10.0%, and still more preferably 5.0%.
Sr ²⁺ can be contained in the glass using, for example, Sr (NO ₃ ) ₂ , SrF ₂ or the like as a raw material.

<Ln ³⁺ >
The optical glass of the present invention preferably contains Ln ³⁺ . Ln ³⁺ means at least one selected from the group consisting of Y ³⁺ , La ³⁺ , Gd ³⁺ , Yb ³⁺ and Lu ³⁺ . The Lu ³⁺ content means the total content of these five ions.
The content of Ln ³⁺ is preferably 0 to 10.0%. This is because when the content is in such a range, the refractive index of the glass is increased and the dispersion becomes low. The content of Ln ³⁺ is more preferably 1.5%, still more preferably 2.0%, more preferably 9.0%, more preferably 8.0%, still more preferably 7.0%. Is the upper limit.

<Y ³⁺ >
The optical glass of the present invention may contain Y ³⁺ as one of Ln ³⁺ . Y ³⁺ has the property of increasing the refractive index of the glass, making it difficult for the anomalous dispersion to decrease, and increasing the devitrification resistance while suppressing an increase in the glass transition point (Tg).
Since such properties are strengthened, the content of Y ³⁺ is preferably 1.5%, more preferably 2.0% as a lower limit, preferably 9.0%, more preferably 8.0%, Preferably, the upper limit is 7.0%.
Y ³⁺ can be contained in the glass using, for example, Y ₂ O ₃ , YF ₃ or the like as a raw material.

<La ³⁺ >
The optical glass of the present invention may contain La ³⁺ as one of Ln ³⁺ . La ³⁺ has properties that increase the refractive index of the glass and make it difficult to reduce anomalous dispersion.
Since such properties are strengthened, the La ³⁺ content is preferably 1.5%, more preferably 2.0% as the lower limit, preferably 9.0%, more preferably 8.0%, Preferably, the upper limit is 7.0%.
La ³⁺ can be contained in the glass using, for example, La ₂ O ₃ , LaF ₃ or the like as a raw material.

<Gd ³⁺ >
The optical glass of the present invention may contain Gd ³⁺ as one of Ln ³⁺ . Gd ³⁺ has the properties of increasing the refractive index of glass, making it difficult to reduce anomalous dispersion, and further improving devitrification resistance.
Since such properties are strengthened, the content of Gd ³⁺ is preferably 1.0%, more preferably 1.5%, more preferably 2.0% as the lower limit, preferably 9.0%, more preferably The upper limit is 8.0%, more preferably 7.0%.
Gd ³⁺ can be contained in the glass using, for example, Gd ₂ O ₃ , GdF ₃ or the like as a raw material.

<Yb ³⁺ >
The optical glass of the present invention may contain Yb ³⁺ as one of Ln ³⁺ . Yb ³⁺ has the properties of increasing the refractive index of glass, making it difficult to reduce anomalous dispersibility, and further improving devitrification resistance.
Since such properties are strengthened, the content of Yb ³⁺ is preferably 1.5%, more preferably 2.0% as a lower limit, preferably 9.0%, more preferably 8.0%, Preferably, the upper limit is 7.0%.
Yb ³⁺ can be contained in the glass using, for example, Yb ₂ O ₃ as a raw material.

<Lu ³⁺ >
The optical glass of the present invention may contain Lu ³⁺ as one of Ln ³⁺ . Lu ³⁺ has the properties of increasing the refractive index of glass, making it difficult to reduce anomalous dispersibility, and further improving resistance to devitrification.
Since such properties are strengthened, the Lu ³⁺ content is preferably 1.5%, more preferably 2.0% as a lower limit, preferably 9.0%, more preferably 8.0%, Preferably, the upper limit is 7.0%.
Lu ³⁺ can be contained in the glass using, for example, Lu ₂ O ₃ as a raw material.

<Si ⁴⁺ >
The optical glass of the present invention may contain Si ⁴⁺ as an optional component. Si ⁴⁺ has the property of increasing the devitrification resistance when contained in a predetermined amount, increasing the refractive index, and decreasing the degree of wear and improving the workability.
Since such properties are strengthened, the Si ⁴⁺ content is preferably 10.0%, more preferably 8.0%, and even more preferably 5.0%.
Si ⁴⁺ can be contained in the glass by using, for example, SiO ₂ , K ₂ SiF ₆ , Na ₂ SiF ₆ or the like as a raw material.

<B ³⁺ >
The optical glass of the present invention may contain B ³⁺ as an optional component. B ³⁺ increases resistance to devitrification and increases the refractive index when it is contained in a predetermined amount, while lowering the degree of wear and improving workability, making it difficult to deteriorate the chemical durability of the glass. It has the property of reducing the formation of striae.
Since such properties increase, the B ³⁺ content is preferably 10.0%, more preferably 8.0%, and even more preferably 5.0%.
B ³⁺ can be contained in the glass using, for example, H ₃ BO ₃ , Na ₂ B ₄ O ₇ , BPO ₄ or the like as a raw material.

<Rn ⁺ >
In the optical glass of the present invention, the total content of Rn ⁺ (Rn ⁺ is at least one selected from the group consisting of Li ⁺ , Na ⁺ and K ⁺ ) is preferably 20.0% or less, It is more preferably 0% or less, and further preferably 10.0%.

<Li ⁺ >
The optical glass of the present invention may contain Li ⁺ as an optional component. Li ⁺ has the property of lowering the glass transition point (Tg) while maintaining devitrification resistance during glass formation.
Since such properties are strengthened, the upper limit of the content of Li ⁺ is preferably 20.0%, more preferably 15.0%, and still more preferably 10.0%.
Li ⁺ can be contained in the glass using, for example, Li ₂ CO ₃ , LiNO ₃ , LiF or the like as a raw material.

<Na ⁺ >
The optical glass of the present invention may contain Na ⁺ as an optional component. Na ⁺ has the property of lowering the glass transition point (Tg) while maintaining devitrification resistance during glass formation.
Since such properties increase, the upper limit of the Na ⁺ content is preferably 10.0%, more preferably 8.0%, and even more preferably 5.0%.
Na ⁺ can be contained in the glass by using, for example, Na ₂ CO ₃ , NaNO ₃ , NaF, Na ₂ SiF ₆ or the like as a raw material.

<K ⁺ >
The optical glass of the present invention may contain K ⁺ as an optional component. K ⁺ has the property of lowering the glass transition point (Tg) while maintaining devitrification resistance during glass formation.
Since such properties are strengthened, the K ⁺ content is preferably 10.0%, more preferably 8.0%, and even more preferably 5.0%.
K ⁺ can be contained in the glass using, for example, K ₂ CO ₃ , KNO ₃ , KF, KHF ₂ , K ₂ SiF ₆ or the like as a raw material.

<Zn ²⁺ >
The optical glass of the present invention may contain Zn ²⁺ as an optional component. Zn ²⁺ has the property of increasing the devitrification resistance of the glass when contained in a predetermined amount. Moreover, it has the property of suppressing the degree of wear of glass.
Since such properties are enhanced, the Zn ²⁺ content is preferably 0% to 40.0%. The Zn ²⁺ content is more preferably 1.0%, more preferably 15.0%, more preferably 16.0%, still more preferably 17.0%, and more preferably 38.0%. More preferably, the upper limit is 37.0%, more preferably 7.0%, and still more preferably 5.0%.
Zn ²⁺ can be contained in the glass by using, for example, Zn (PO ₃ ) ₂ , ZnO, ZnF ₂ or the like as a raw material.

<Nb ⁵⁺ >
The optical glass of the present invention may contain Nb ⁵⁺ as an optional component. Nb ⁵⁺ has the properties of increasing the refractive index of the glass, increasing the chemical durability, further suppressing the decrease in the Abbe number, and suppressing the increase in the melting temperature.
Since such properties increase, the Nb ⁵⁺ content is preferably 10.0%, more preferably 8.0%, and even more preferably 5.0%.
Nb ⁵⁺ can be contained in the glass using, for example, Nb ₂ O ₅ as a raw material.

<Ti ⁴⁺ >
The optical glass of the present invention may contain Ti ⁴⁺ as an optional component. Ti ⁴⁺ has the property of increasing the refractive index of glass and reducing coloring.
Since such properties are strengthened, the Ti ⁴⁺ content is preferably 10.0%, more preferably 8.0%, and even more preferably 5.0% .
Ti ⁴⁺ is a raw material as, for example, with TiO ₂ or the like can be contained in the glass.

<Zr ⁴⁺ >
The optical glass of the present invention may contain Zr ⁴⁺ as an optional component. Zr ⁴⁺ has the property of increasing the refractive index of the glass and increasing the mechanical strength of the glass.
Since such properties are strengthened, the Zr ⁴⁺ content is preferably 10.0%, more preferably 8.0%, and even more preferably 5.0%.
Zr ⁴⁺ can be contained in the glass using, for example, ZrO ₂ , ZrF ₄ or the like as a raw material.

<Ta ⁵⁺ >
The optical glass of the present invention may contain Ta ⁵⁺ as an optional component. Ta ⁵⁺ has the property of increasing the refractive index of glass.
Since such properties increase, the upper limit of the Ta ⁵⁺ content is preferably 10.0%, more preferably 8.0%, and even more preferably 5.0%.
Ta ⁵⁺ can be contained in the glass using, for example, Ta ₂ O ₅ as a raw material.

<W ⁶⁺ >
The optical glass of the present invention may contain W ⁶⁺ as an optional component. W ⁶⁺ has the property of increasing the refractive index of the glass and further suppressing the decrease in the Abbe number.
Since such properties increase, the upper limit of the W ⁶⁺ content is preferably 10.0%, more preferably 8.0%, and even more preferably 5.0%.
W ⁶⁺ can be contained in the glass using, for example, WO ₃ as a raw material.

<Ge ⁴⁺ >
The optical glass of the present invention may contain Ge ⁴⁺ as an optional component. Ge ⁴⁺ has the property of increasing the refractive index of glass and increasing the devitrification resistance of glass.
Since such properties become remarkable, the content of Ge ⁴⁺ is preferably 10.0%, more preferably 8.0%, and still more preferably 5.0%.
Ge ⁴⁺ can be contained in the glass using, for example, GeO ₂ as a raw material.

<Bi ³⁺ >
The optical glass of the present invention may contain Bi ³⁺ as an optional component. Bi ³⁺ has the property of increasing the refractive index of the glass and lowering the glass transition point.
Since such properties are strengthened, the Bi ³⁺ content is preferably 10.0%, more preferably 8.0%, and even more preferably 5.0%.
Bi ³⁺ can be contained in the glass using, for example, Bi ₂ O ₃ as a raw material.

<Te ⁴⁺ >
The optical glass of the present invention may contain Te ⁴⁺ as an optional component. Te ⁴⁺ has the property of increasing the refractive index of glass, making it difficult to devitrify, and suppressing coloring.
Since such properties are strengthened, the Te ⁴⁺ content is preferably 15.0%, more preferably 10.0%, more preferably 8.0%, and even more preferably 5.0%. .
Te ⁴⁺ can be contained in the glass using, for example, TeO ₂ as a raw material.

[About anion components]
<F ^->
The optical glass of the present invention contains F ⁻ . F ⁻ has the properties of increasing the anomalous dispersion and Abbe number of the glass and making the glass difficult to devitrify.
Since such properties are strengthened, the content of F ⁻ is preferably 20.0 to 95.0%. The content of F ⁻ is preferably 22.0%, more preferably 23.0%, more preferably 24.0%, preferably 70.0%, more preferably 65.0%, more preferably Is 60.0%, more preferably 59.0%, more preferably 58.0%.
F ⁻ can be contained in the glass by using fluorides of various cationic components such as AlF ₃ , MgF ₂ , and BaF ₂ as a raw material.

< ^O2- >
The optical glass of the present invention contains O ²⁻ . O ²⁻ has a property of suppressing an increase in the degree of wear and is a component necessary for forming a network structure.
The total of the content of O ^{2− and} the content of F ⁻ is preferably 98.0% or more in terms of anion%, more preferably 99.0% or more, and 100%. Further preferred. This is because stable glass can be obtained.
O ²⁻ is a raw material such as oxides of various cationic components such as Al ₂ O ₃ , MgO and BaO, and phosphoric acids of various cationic components such as Al (PO) ₃ , Mg (PO) ₂ and Ba (PO) _2. It can be contained in the glass using a salt or the like.

[About ingredients that should not be contained]
Next, components that should not be contained in the optical glass of the present invention and components that are not preferably contained will be described.

  If necessary, other components can be added to the optical glass of the present invention as long as the properties of the glass of the present invention are not impaired.

  In addition, except for Ti, Zr, Nb, W, La, Gd, Y, Yb and Lu, the transition metal cations such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo are each independently Or, even when contained in a small amount in combination, the glass is colored and has the property of causing absorption at a specific wavelength in the visible range. Therefore, particularly in optical glass using a wavelength in the visible range, it is preferable that the glass is not substantially contained. .

  Furthermore, Pb, Th, Cd, Tl, Os, Be and Se cations have tended to refrain from being used as harmful chemicals in recent years, not only in the glass manufacturing process, but also in the processing process and disposal after commercialization. Until then, environmental measures are required. Therefore, when importance is placed on the environmental impact, it is preferable not to substantially contain them except for inevitable mixing. As a result, the optical glass is substantially free of substances that pollute the environment. Therefore, the optical glass can be manufactured, processed, and discarded without taking special environmental measures.

[Production method]
The method for producing the optical glass of the present invention is not particularly limited. For example, the above raw materials are uniformly mixed so that each component is within a predetermined content range, and the prepared mixture is put into a quartz crucible, an alumina crucible or a platinum crucible, and is roughly melted, and then a platinum crucible, a platinum alloy Stir in a crucible or iridium crucible for 2-10 hours at 900-1200 ° C, stir to homogenize, blow out bubbles, etc., then lower the temperature to 850 ° C or lower, then stir to finish and stir It is possible to manufacture by removing the above, casting into a mold and slow cooling.

[Physical properties]
The optical glass of the present invention is characterized by a partial dispersion ratio (θg, F). Therefore, it is easy to obtain an optical glass capable of correcting chromatic aberration with high accuracy.
The partial dispersion ratio (θg, F) is 0.530 or more, preferably 0.533 or more, more preferably 0.538 or more, and further preferably 0.540 or more.
The partial dispersion ratio (θg, F) means a value obtained by measurement based on Japan Optical Glass Industry Association Standard JOGIS01-2003.
Moreover, the partial dispersion ratio as used in the field of this invention shall mean the partial dispersion ratio in a short wavelength region.

The optical glass of the present invention has high anomalous dispersion (Δθg, F). Therefore, it is easy to obtain a lens that can correct chromatic aberration with high accuracy.
The anomalous dispersion (Δθg, F) is preferably 0.006 or more, more preferably 0.008 or more, more preferably 0.010 or more, and more preferably 0.011 or more. Preferably, it is 0.012 or more, more preferably 0.013 or more.

Here, the partial dispersion ratio (θg, F) and the anomalous dispersion (Δθg, F) will be described, and then the physical properties of the optical glass of the present invention will be described in more detail.
First, the partial dispersion ratio (θg, F) will be described.
The partial dispersion ratio (θg, F) indicates the ratio of the difference in refractive index between two wavelength ranges in the wavelength dependence of the refractive index, and is expressed by the following formula (1).
θg, F = ( _ng− n _F ) / (n _F −n _C ) (1)
Here, _ng means the g-line (435.83 nm), n _F means the F-line (486.13 nm), and n _C means the refractive index of the C-line (656.27 nm).
When the relationship between the partial dispersion ratio (θg, F) and the Abbe number (νd) is plotted on an XY graph, in the case of general optical glass, it is plotted on a straight line called a normal line. Become. The normal line is the XY graph (on the Cartesian coordinates) where the partial dispersion ratio (θg, F) is taken on the vertical axis and the Abbe number (νd) is taken on the horizontal axis, and the partial dispersion ratio and Abbe number of NSL7 and PBM2 It means a straight line going up to the right connecting the two plotted points (see FIG. 1). Normal glass, which is the standard for the normal line, differs depending on the optical glass manufacturer, but each company defines it with almost the same tilt and intercept (NSL7 and PBM2 are optical glasses manufactured by OHARA, Inc. The number (νd) is 60.5, the partial dispersion ratio (θg, F) is 0.5436, the Abbe number (νd) of PBM2 is 36.3, and the partial dispersion ratio (θg, F) is 0.5828).

  For such a partial dispersion ratio (θg, F), anomalous dispersion (Δθg, F) means that the plot of partial dispersion ratio (θg, F) and Abbe number (νd) is in the vertical axis direction from the normal line. It shows how far away. An optical element made of glass having a large anomalous dispersion (Δθg, F) has a property capable of correcting chromatic aberration caused by other lenses in a wavelength range near blue.

  Further, conventionally, in the medium to low dispersion region (region where the Abbe number is about 55 or more), the anomalous dispersion (Δθg, F) tends to increase as the Abbe number (νd) increases. Furthermore, it tends to be difficult to maintain the anomalous dispersibility at a high level while reducing the degree of wear.

The inventor has intensively studied and succeeded in developing an optical glass in which the value of the anomalous dispersion (Δθg, F) with respect to the Abbe number (νd) is higher than that of the conventional one.
For example, in the case of an optical glass having a more preferable mode shown later as an example, when the Abbe number (νd) is about 68 to 75, the partial dispersion ratio (θg, F) becomes 0.54 or more, and anomalous dispersion ( An optical glass having Δθg, F) of 0.011 or more can be obtained. Such values of the partial dispersion ratio (θg, F) and anomalous dispersion (Δθg, F) are significantly higher than those of the conventional one having the same Abbe number (νd).

The optical glass of the present invention has a high refractive index (nd) and low dispersion (high Abbe number).
The refractive index (nd) is 1.50 or more, preferably 1.51 or more, more preferably 1.52 or more, and further preferably 1.524 or more.
The Abbe number (νd) is preferably 65 or more, more preferably 68 or more, more preferably 70 or more, and further preferably 71 or more.
Since the optical glass of the present invention has such a refractive index (nd) and Abbe number (νd), the degree of freedom in optical design is widened, and a large amount of light can be obtained even if the device is made thinner. Can do.
The refractive index (nd) and Abbe number (νd) mean values obtained by measurement based on the Japan Optical Glass Industry Association Standard JOGIS01-2003.

The optical glass of the present invention is excellent in devitrification resistance. Accordingly, it is difficult to devitrify even if reheating is performed during press molding.
Since the optical glass of the present invention is excellent in devitrification resistance, the crystallization temperature (Tc) is not observed by DTA measurement.

[Preforms and optical elements]
The optical glass of the present invention is useful for various optical elements and optical designs. Among them, a preform is formed from the optical glass of the present invention, and polishing, precision press molding, etc. are performed on the preform. It is preferable to produce an optical element such as a lens, a prism, or a mirror using the means. As a result, when used in optical devices that transmit visible light to optical elements such as cameras and projectors, the optical system in these optical devices can be miniaturized while realizing high-definition and high-precision imaging characteristics. You can plan. Here, the method for producing the preform material is not particularly limited. For example, a glass gob forming method described in JP-A-8-319124 and an optical glass manufacturing method and manufacturing apparatus described in JP-A-8-73229 are used. Thus, a method of manufacturing a preform material directly from molten glass can also be used, and a method of manufacturing by performing cold processing such as grinding and polishing on a strip material formed from optical glass can also be used.

  The glass composition, refractive index (nd), Abbe number (νd), partial dispersion ratio (θg, F) and anomalous dispersion (Δθg, F) of Examples (No. 1 to No. 6) of the present invention Shown in Table 1.

  The optical glasses of Examples (No. 1 to No. 6) of the present invention are ordinary fluorophosphates such as oxides, carbonates, nitrates, fluorides, metaphosphate compounds, etc. corresponding to the raw materials of the respective components. The high-purity raw material used for the glass is selected, weighed so as to have the composition ratio of each example shown in Table 1, and mixed uniformly, and then put into a platinum crucible, and the melting difficulty of the glass composition Depending on the temperature, melt in a temperature range of 900-1200 ° C in an electric furnace for 2-10 hours, stir and homogenize to blow out bubbles, etc., then lower the temperature to 850 ° C or lower, cast into a mold, and slowly cool Glass was produced.

  Here, with respect to the refractive index (nd), Abbe number (νd) and partial dispersion ratio (θg, F) of the optical glass of Examples (No. 1 to No. 6), Japan Optical Glass Industry Association Standard JOGIS01-2003 Measured based on The glass used in this measurement was annealed under a slow cooling furnace with a slow cooling rate of −25 ° C./hr. From the difference between the value of the partial dispersion ratio (θg, F) on the normal line in FIG. 1 and the value of the measured partial dispersion ratio (θg, F) in the measured Abbe number (νd), Dispersibility (Δθg, F) was determined.

  The devitrification resistance was judged by whether or not the crystallization temperature (Tc) was observed by DTA measurement. If Tc is not observed, it is considered that even if reheating for press molding is performed, devitrification does not occur, that is, stability in reheat press is excellent.

As shown in Table 1, all of the optical glasses of the examples of the present invention had a partial dispersion ratio (θg, F) of 0.540 or more and a refractive index (nd) of 1.54 or more. It was. Further, in all cases, the anomalous dispersion (Δθg, F) was 0.011 or more.
Such values of the partial dispersion ratio (θg, F) and anomalous dispersion (Δθg, F) are significantly higher than those of the conventional one having the same Abbe number (νd).

  In any case, the crystallization temperature (Tc) was not observed.

Furthermore, using the optical glass of the example of the present invention, after forming a preform for polishing, grinding and polishing were performed to form lenses and prisms. In addition, a precision press-molding preform was formed using the optical glass of the example of the present invention, and the precision press-molding preform was precision press-molded into a lens and a prism. In either case, it could be processed into various lens and prism shapes.

Claims (6)

P ⁵⁺ , Al ³⁺ , R ²⁺ (R ²⁺ is at least one selected from the group consisting of Mg ²⁺ , Ca ²⁺ , Sr ²⁺ and Ba ²⁺ ), B ³⁺ And Ln ³⁺ (Ln ³⁺ is at least one selected from the group consisting of Y ³⁺ , La ³⁺ , Gd ³⁺ , Yb ³⁺ and Lu ³⁺ ) ,
In terms of cation%, the P ⁵⁺ content is 22.0-55.0%, the Al ³⁺ content is 3.0-15.0%, and the Ca ²⁺ content is 14.0-24. 0%, R2 ⁺ content is 32.0-58.0% , ^{B3 +} content is 10% or less, and Ln3 ⁺ total content is 1-10.0% ,
As an anion component, F ^- containing and O ^2-,
An optical glass having a refractive index (nd) of 1.50 or more and an Abbe number (νd) of 65 or more. The optical glass according to claim 1, wherein the content of F ⁻ is 20.0 to 95.0% in terms of anion%. An optical element formed of the optical glass according to claim 1 or 2. Claim 1 or preform for polishing machining and / or precision press molding comprised of the optical glass according to 2. An optical element obtained by polishing the preform according to claim 4 . An optical element obtained by precision pressing the preform according to claim 4 .

Images