JP5836471B2 - Optical glass - Google Patents

Description

  The present invention relates to an optical glass having a high refractive index and a low dispersion characteristic, a glass gob for press molding made of the optical glass, an optical element, a manufacturing method thereof, and a manufacturing method of an optical element blank.

A lens made of high refractive index and low dispersion glass can be combined with a lens made of ultra low dispersion glass to make the optical system compact while correcting chromatic aberration. Therefore, it occupies a very important position as an optical element constituting a projection optical system such as an imaging optical system or a projector.
Patent Document 1 discloses such a high refractive index and low dispersion glass.

Japanese Patent Laid-Open No. 55-60039

By the way, the high refractive index and low dispersion glass has a relatively high amount of the high refractive index imparting component and a relatively small amount of the glass network forming component, so that the glass stability is lowered and devitrified in the manufacturing process. I have problems such as becoming easier.
Moreover, there is also a problem that when the amount of the high refractive index imparting component is increased, the coloring of the glass becomes remarkable.

  The present invention provides an optical glass having a low refractive index, an extremely high refractive index, excellent glass stability, and little coloring, and a glass gob for press molding and an optical element blank made of the optical glass. It is an object of the present invention to provide an optical element blank and an optical element manufacturing method.

  As a result of intensive studies to achieve the above object, the present inventors have found that the object can be achieved by an optical glass having a specific glass composition, refractive index, and Abbe number, and based on this finding. The present invention has been completed.

That is, the present invention
(1) Oxide glass, expressed as cation%,
Si ⁴⁺ 1 ~30%,
B ³⁺ 13 to 45 %,
Li ⁺ , Na ⁺ and K ⁺ in total less than 5%,
Less than 5% in total Mg ²⁺ , Ca ²⁺ and Sr ²⁺
Ba ²⁺ 0-8%,
Zn ²⁺ 0.1~ 12%,
La ³⁺ 10~ 40%,
Gd ³⁺ 0-20%,
Y ³⁺ 0.25-15%,
Yb ³⁺ 0-10%,
Zr ⁴⁺ 1 ~20%,
Ti ⁴⁺ 1 ~22%,
Nb ⁵⁺ 0.1-20 %,
Ta ⁵⁺ 0-8%,
W ⁶⁺ 0-5%,
Ge ⁴⁺ 0-8%,
Bi ³⁺ 0-10%,
Al ³⁺ 0-10%,
Wherein the content of the cation ratio of Si ⁴⁺ / B ³⁺ is less than 1.0 of Si ⁴⁺ to the content of B ^3+, the total content of in terms of oxide Nb ₂ O ₅ and Ta ₂ O ₅ The amount is less than 14% by weight,
An optical glass having a refractive index nd of 1.92 to 2.2, an Abbe number νd of 25 to 45, and a glass transition temperature Tg of 630 ° C. or higher;
( 2 ) The optical glass according to (1), wherein the coloring degree λ70 is less than 470 nm,
( 3 ) The optical glass according to the above item (1) or (2) , wherein the partial dispersion ratio Pg, F and the Abbe number νd satisfy the relationship of the following equation (1):
Pg, F ≦ −0.0017 × νd + 0.660 (1)
( 4 ) A glass gob for press molding, comprising the optical glass described in any one of the above items (1) to ( 3 ),
( 5 ) An optical element comprising the optical glass according to any one of (1) to ( 3 ) above,
Is to provide.

  According to the present invention, an optical glass having a refractive index nd of 1.92 or more and an Abbe number νd of 25 or more and a low dispersion while having an extremely high refractive index, excellent glass stability, and relatively little coloring. Providing, providing a glass gob for press molding and an optical element blank made of the optical glass, and methods for manufacturing the optical element blank and the optical element can be provided.

  According to the optical element and the optical element produced from the press molding glass gob or the optical element blank, for example, a lens, a compact optical system for correcting chromatic aberration is provided by combining with a lens made of a high refractive index and high dispersion glass. You can also.

  Further, according to a preferred aspect of the optical glass of the present invention, the optical glass having the above-mentioned optical characteristics and having a small partial dispersion ratio Pg, F as compared with a glass having the same Abbe number νd and suitable for higher-order color correction. Can also be provided. Taking advantage of these properties, an optical element suitable for high-order chromatic aberration correction can be provided by combining with an optical element made of high refractive index and high dispersion optical glass.

[Optical glass]
First, the optical glass of the present invention will be described.
The optical glass of the present invention is
Oxide glass, expressed as cation%,
Si ⁴⁺ 0-30%,
B ³⁺ 10-55%,
Li ⁺ , Na ⁺ and K ⁺ in total less than 5%,
Less than 5% in total Mg ²⁺ , Ca ²⁺ and Sr ²⁺
Ba ²⁺ 0-8%,
Zn ²⁺ 0.1-15%,
La ³⁺ 10-50%,
Gd ³⁺ 0-20%,
Y ³⁺ 0-15%,
Yb ³⁺ 0-10%,
Zr ⁴⁺ 0-20%,
Ti ⁴⁺ 0.1-22%,
Nb ⁵⁺ 0-20%,
Ta ⁵⁺ 0-8%,
W ⁶⁺ 0-5%,
Ge ⁴⁺ 0-8%,
Bi ³⁺ 0-10%,
Al ³⁺ 0-10%,
Wherein the cation ratio of the content of Si ⁴⁺ to the content of B ³⁺ Si ⁴⁺ / B ³⁺ is less than 1.0,
The total content of Nb ₂ O ₅ and Ta ₂ O ₅ in terms of oxide is less than 14% by mass,
An optical glass having a refractive index nd of 1.92 to 2.2 and an Abbe number νd of 25 to 45.

(Reason for limitation of composition range)
The reasons for limiting the composition range will be described, but unless otherwise specified, the content and total content of each component are expressed in cation%.

Si ⁴⁺ is a network-forming cation, and is an effective component for maintaining glass stability, maintaining viscosity suitable for forming molten glass, and improving chemical durability. When the amount exceeds 30%, While it becomes difficult to achieve a desired refractive index, the liquidus temperature and the glass transition temperature increase. In addition, problems such as difficulty in realizing a desired Abbe number, deterioration in glass meltability, and deterioration in devitrification resistance occur. Therefore, the content of Si ⁴⁺ is set to 0 to 30%. The preferable upper limit of the content of Si ⁴⁺ is 25%, the more preferable upper limit is 23%, the further preferable upper limit is 20%, the more preferable upper limit is 18%, the still more preferable upper limit is 15%, and the still more preferable upper limit is 12%. is there. In order to obtain the Si ⁴⁺ -containing effect, the preferable lower limit of the Si ⁴⁺ content is 1%, the more preferable lower limit is 3%, the still more preferable lower limit is 4%, and the still more preferable lower limit is 5%, even more preferable. The lower limit is 6%.

B ³⁺ is a network-forming cation, and is an essential component effective for maintaining the meltability of the glass, lowering the liquidus temperature and reducing the glass stability, and reducing the dispersion. When the amount is less than 10%, the glass stability is lowered and the above effect cannot be obtained. When the amount exceeds 55%, it is difficult to satisfy a desired refractive index and the chemical durability is deteriorated. Therefore, the content of B ³⁺ is set to 10 to 55%. A preferable upper limit of the content of B ³⁺ is 50%, a more preferable upper limit is 48%, a further preferable upper limit is 45%, a still more preferable upper limit is 43%, a still more preferable upper limit is 40%, a still more preferable upper limit is 35%, An even more preferable upper limit is 32%, and an even more preferable upper limit is 30%. A preferable lower limit of the content of B ³⁺ is 13%, a more preferable lower limit is 15%, a further preferable lower limit is 18%, and a more preferable lower limit is 20%, a more preferred lower limit is 21%, and a still more preferred lower limit is 22%.

Incidentally, while maintaining low dispersion, reduction of the liquidus temperature, devitrification resistance and improved meltability improved, from maintaining the viscosity suitable for molding, the Si ⁴⁺ to the content of B ³⁺ The cation ratio Si ⁴⁺ / B ³⁺ of the content is less than 1. A preferable upper limit of the cation ratio Si ⁴⁺ / B ³⁺ is 0.5. A preferable lower limit of the cation ratio Si ⁴⁺ / B ³⁺ is 0.03.

Li ⁺ , Na ⁺ and K ⁺ are optional components that serve to improve the meltability and lower the glass transition temperature. When the total content of Li ⁺ , Na ⁺ and K ⁺ is 5% or more, it becomes difficult to achieve a desired refractive index, the liquidus temperature rises, and the glass stability and chemical durability also decrease. Therefore, the total content of Li ⁺ , Na ⁺ and K ⁺ is set to less than 5%. A preferable range of the total content of Li ⁺ , Na ⁺ and K ⁺ is less than 3%, a more preferable range is less than 2%, and a further preferable range is less than 1%, and it is even more preferable not to include the alkali metal component.

Mg ²⁺ , Ca ²⁺ and Sr ²⁺ work to improve the meltability of the glass and lower the glass transition temperature Tg. Moreover, the defoaming effect is also acquired by introduce | transducing into glass in the form of nitrate and sulfate. However, when the total content of Mg ²⁺ , Ca ²⁺ and Sr ²⁺ exceeds 5%, the liquidus temperature rises, devitrification resistance deteriorates, the refractive index decreases, and the chemical durability also increases. It will get worse. Therefore, the total content of Mg ²⁺ , Ca ²⁺ and Sr ²⁺ is set to less than 5%. The preferred range of the total content of Mg ²⁺ , Ca ²⁺ and Sr ²⁺ is less than 3%, more preferred range is less than 2%, even more preferred range is less than 1%, and no alkaline earth metal component is contained. Is more preferable.

Ba ²⁺ improves the meltability of the glass, and a defoaming effect can also be obtained by introducing it in the form of carbonate or nitrate. However, when the Ba ²⁺ content exceeds 8%, the liquidus temperature rises, the glass stability decreases, and it becomes difficult to achieve a desired refractive index. In addition, chemical durability is also deteriorated. Therefore, the content of Ba ²⁺ is set to 0 to 8%. A preferable range of the Ba ²⁺ content is 0 to 7, a more preferable range is 0 to 6%, and a further preferable range is 0 to 5%. In order to achieve the object of the present invention, the Ba ²⁺ content may be 3% or less, 2% or less, 1% or less, or zero.

Zn ²⁺ is an essential component useful for realizing a high refractive index and low dispersion characteristic, and functions to improve the meltability and devitrification resistance of the glass and lower the liquidus temperature and the glass transition temperature. If the amount is less than 0.1%, the refractive index decreases, the liquidus temperature rises, and devitrification resistance deteriorates. On the other hand, if the amount exceeds 15%, it becomes difficult to achieve a desired refractive index. Therefore, the Zn ²⁺ content is set to 0.1 to 15%. The preferred upper limit of the Zn ²⁺ content is 14%, the more preferred upper limit is 13%, the still more preferred upper limit is 12%, the still more preferred upper limit is 11%, the still more preferred upper limit is 10%, the still more preferred upper limit is 7%, An even more preferable upper limit is 6%, and an even more preferable upper limit is 5%. A preferable lower limit of the Zn ²⁺ content is 0.3%, a more preferable lower limit is 0.5%, and a further preferable lower limit is 1%. .

La ³⁺ is essential for realizing a high refractive index and low dispersion characteristic, and also serves to improve chemical durability. If the amount is less than 10%, it becomes difficult to obtain a desired refractive index, and if it exceeds 50%, the liquidus temperature rises and the devitrification resistance deteriorates. Therefore, the La ³⁺ content is 10 to 50%. The preferable upper limit of the content of La ³⁺ is 48%, more preferable upper limit is 45%, further preferable upper limit is 43%, still more preferable upper limit is 40%, still more preferable upper limit is 38%, still more preferable upper limit is 37%, An even more preferred upper limit is 36%, an even more preferred upper limit is 35%, a preferred lower limit for the content of La ³⁺ is 13%, a more preferred lower limit is 15%, a still more preferred lower limit is 18%, and a more preferred lower limit is 20%, a more preferred lower limit is 21%, and a still more preferred lower limit is 22%.

Gd ³⁺ works by coexisting with La ³⁺ to lower the liquidus temperature, greatly improve resistance to devitrification, and improve chemical durability. However, if the amount exceeds 20%, the liquidus temperature rises and the devitrification resistance deteriorates. Therefore, the content of Gd ³⁺ is set to 0 to 20%. A preferred upper limit of the content of Gd ³⁺ is 18%, a more preferred upper limit is 15%, a still more preferred upper limit is 13%, a still more preferred upper limit is 12%, a still more preferred upper limit is 10%, a still more preferred upper limit is 9%, An even more preferable upper limit is 8%, an even more preferable upper limit is 7%, a preferable lower limit of the content of Gd ³⁺ is 0.1%, a more preferable lower limit is 0.5%, and a further preferable lower limit is 1%. A more preferred lower limit is 2%.

Y ³⁺ coexists with La ³⁺ to lower the liquidus temperature, greatly improve devitrification resistance, and improve chemical durability. If the amount exceeds 15%, Phase temperature rises and devitrification resistance deteriorates. Therefore, the content of Y ³⁺ is set to 0 to 15%. A preferred range for the content of Y ³⁺ is 0 to 13%, a more preferred range is 0 to 10%, a further preferred range is 0 to 8%, a more preferred range is 0 to 7%, and a still more preferred range is 0 to 5%. %, And an even more preferable range is 0 to 4%.

When Yb ³⁺ coexists with La ³⁺ , the liquidus temperature is lowered, the devitrification resistance is greatly improved, and the chemical durability is improved. If the amount exceeds 10%, the liquidus temperature rises and the devitrification resistance deteriorates. Therefore, the content of Yb ³⁺ is set to 0 to 10%. A preferred range for the content of Yb ³⁺ is 0 to 5%, a more preferred range is 0 to 3%, a further preferred range is 0 to 1%, and it is more preferred that no Yb ³⁺ is contained.

Zr ⁴⁺ functions to increase the refractive index and improve chemical durability. Even if it is introduced in a small amount, an excellent effect can be obtained. However, if the amount exceeds 20%, the glass transition temperature and the liquidus temperature increase, and the devitrification resistance decreases. Therefore, the content of Zr ⁴⁺ is set to 0 to 20%. A preferable upper limit of the content of Zr ⁴⁺ is 18%, a more preferable upper limit is 16%, a further preferable upper limit is 14%, a still more preferable upper limit is 12%, a still more preferable upper limit is 10%, a still more preferable upper limit is 8%, An even more preferable upper limit is 7%, a preferable lower limit of the content of Zr ⁴⁺ is 1%, a more preferable lower limit is 2%, and a further preferable lower limit is 3%.

Ti ⁴⁺ serves to increase the refractive index and improve chemical durability and resistance to devitrification. If the content is less than 0.1%, the above effect cannot be obtained, and if it exceeds 22%, it becomes difficult to obtain a desired Abbe number, and the glass transition temperature and the liquidus temperature are increased. Devitrification deteriorates. Therefore, the content of Ti ⁴⁺ is set to 0.1 to 22%. The preferable upper limit of the content of Ti ⁴⁺ is 21%, the more preferable upper limit is 20%, the further preferable upper limit is 19%, the more preferable upper limit is 18%, the still more preferable upper limit is 17%, and the further preferable upper limit is 16%, and a more preferred upper limit is 15%. The preferred lower limit of the Ti ⁴⁺ content is 1%, the more preferred lower limit is 3%, the still more preferred lower limit is 5%, the still more preferred lower limit is 8%, the still more preferred lower limit is 10%, the still more preferred lower limit is 11%, An even more preferred lower limit is 12%.
Particularly when the refractive index nd is 1.968 or more, the content of Ti ⁴⁺ is preferably 5% or more, more preferably 10% or more, and further preferably 12% or more, It is more preferable to set it to 13% or more, and it is still more preferable to set it to 14% or more. However, even when the refractive index nd is set to 1.968 or more, the content of Ti ⁴⁺ should be made 21% or less in order to suppress an increase in glass transition temperature, liquidus temperature, and deterioration of devitrification resistance. Preferably, it is more preferably 20% or less, and further preferably 19% or less.

Nb ^{5+ functions} to increase the refractive index, lower the liquidus temperature, and improve devitrification resistance. If the amount exceeds 20%, the liquidus temperature rises, the devitrification resistance deteriorates, it becomes difficult to achieve the desired Abbe number, and the coloring of the glass also increases. Therefore, the Nb ⁵⁺ content is set to 0 to 20%. A preferred upper limit of the Nb ⁵⁺ content is 18%, a more preferred upper limit is 16%, a still more preferred upper limit is 14%, a still more preferred upper limit is 12%, a still more preferred upper limit is 10%, a still more preferred upper limit is 9%, An even more preferred upper limit is 8%. The preferable lower limit of the Nb ⁵⁺ content is 0.1%, the more preferable lower limit is 1%, the still more preferable lower limit is 2%, and the still more preferable lower limit is 3%.

Ta ⁵⁺ realizes a high refractive index and low dispersibility and also functions to increase glass stability. However, since it is an expensive component and its content exceeds 8%, the liquidus temperature rises and the devitrification resistance decreases, so the content of Ta ⁵⁺ is set to 0 to 8%. A preferable range of the content of Ta ⁵⁺ is 0 to 6%, a more preferable range is 0 to 4%, a further preferable range is 0 to 3%, a more preferable range is 0 to 2.5%, and a still more preferable range is 0. -2%, and an even more preferred range is 0-1%. It is particularly preferred not to contain Ta ⁵⁺ .

In the optical glass of the present invention, the contents of Nb ⁵⁺ and Ta ⁵⁺ are converted into oxides in order to suppress increase in liquidus temperature and maintain devitrification resistance, respectively, and Nb ₂ O ₅ and Ta The total content of ₂ O ₅ is limited to less than 14% by weight. From the above viewpoint, the preferable range of the total content of Nb ₂ O ₅ and Ta ₂ O ₅ is 13% by mass or less.

W ⁶⁺ is an optional component that increases the refractive index, lowers the liquidus temperature, and contributes to the improvement of devitrification resistance. However, if its amount exceeds 5%, the liquidus temperature rises and the devitrification resistance increases. As the properties deteriorate, the coloring of the glass also increases. Therefore, the content of W ⁶⁺ is set to 0 to 5%. A preferable range of the content of W ⁶⁺ is 0 to 4%, a more preferable range is 0 to 3%, a further preferable range is 0 to 2%, a more preferable range is 0 to 1%, and no W ⁶⁺ is contained. It is even more preferable.

Ge ⁴⁺ is a network-forming cation, and also functions to increase the refractive index. Therefore, Ge ⁴⁺ is a component that can increase the refractive index while maintaining glass stability. In addition to the Ta component, it is a component desired to refrain from the amount. In the present invention, since the composition is determined as described above, it is possible to achieve both desired optical characteristics and excellent glass stability even if the Ge ⁴⁺ content is suppressed to 8% or less. . Therefore, the content of Ge ⁴⁺ is set to 0 to 8%.
A preferable range of the content of Ge ⁴⁺ is 0 to 6%, a more preferable range is 0 to 4%, a further preferable range is 0 to 2%, and a more preferable range is 0 to 1%. It is particularly preferable not to contain Ge ⁴⁺ , that is, a Ge-free glass.

Bi ³⁺ functions to increase the refractive index and the glass stability, but when its amount exceeds 10%, the light transmittance in the visible region decreases. Therefore, the Bi ³⁺ content is set to 0 to 10%. The preferable range of the Bi ³⁺ content is 0 to 8%, the more preferable range is 0 to 6%, the further preferable range is 0 to 4%, the more preferable range is 0 to 2%, and the still more preferable range is 0 to 1. % And not containing Bi ³⁺ is particularly preferred.

Al ³⁺ works to improve glass stability and chemical durability when it is in a small amount, but when its amount exceeds 10%, the liquidus temperature rises and devitrification resistance deteriorates. Therefore, the content of Al ³⁺ is set to 0 to 10%. A preferable range of the content of Al ³⁺ is 0 to 8%, a more preferable range is 0 to 6%, a further preferable range is 0 to 4%, a more preferable range is 0 to 2%, and a still more preferable range is 0 to 1. %, And it is particularly preferable not to contain Al ³⁺ .

Sb can be added as a refining agent, and even when added in a small amount, it also serves to suppress a decrease in light transmittance due to the inclusion of impurities such as Fe. However, in terms of oxide, it is 1% by mass as Sb ₂ O _3. If it is added beyond the range, the glass is colored, or the strong oxidizing action promotes deterioration of the molding surface of the press mold during press molding. Therefore, in terms of Sb ₂ O ₃ , the amount of Sb added is preferably 0 to 1% by mass, more preferably 0 to 0.5% by mass, and even more preferably 0%.

Sn can also be added as a refining agent. However, if it is added in excess of 1% by mass in terms of SnO ₂ , the glass will be colored or the molding surface of the press mold may deteriorate during precision press molding due to oxidation. It will encourage you. Therefore, the addition amount of Sn in terms of SnO ₂ is preferably 0 to 1% by mass, more preferably 0 to 0.5% by mass, on an external basis.

  In addition, Ce oxides, sulfates, nitrates, and chlorides can be added in small amounts as clarifying agents.

The optical glass of the present invention realizes optical characteristics of high refractive index and low dispersion while maintaining glass stability, and does not need to contain components such as Lu, Hf, Ga, In, and Sc. Since Lu, Hf, Ga, In and Sc are also expensive components, the contents of Lu ³⁺ , Hf ⁴⁺ Ga ³⁺ , In ³⁺ and Sc ³⁺ are preferably suppressed to 0 to 1%, respectively. It is more preferable to suppress it to ˜0.5%. Lu ³⁺ is not introduced, Hf ⁴⁺ is not introduced, Ga ³⁺ is not introduced, In ³⁺ is not introduced, and Sc ³⁺ is not introduced. Each is particularly preferred.

  In consideration of environmental impact, it is preferable not to introduce As, Pb, U, Th, Te, or Cd.

  Furthermore, it is preferable not to introduce a substance that causes coloring such as Cu, Cr, V, Fe, Ni, and Co from the viewpoint of taking advantage of the excellent light transmittance of glass.

The optical glass of the present invention is an oxide glass, and the anion component substantially consists of O ²⁻ . As described above, a small amount of Cl ⁻ and F ⁻ can be added as a fining agent, but the content of O ²⁻ is preferably 98 anion% or more, more preferably 99 anion% or more. , 99.5% anion% or more, more preferably 100 anion%.

(Optical characteristics of optical glass)
The refractive index nd of the optical glass of the present invention is 1.92 to 2.2. The preferable lower limit of the refractive index nd is 1.930, the more preferable lower limit is 1.935, the still more preferable lower limit is 1.940, the preferable upper limit is 2.0, the more preferable upper limit is 1.995, and the further preferable upper limit is 1. 990. Increasing the refractive index is effective in increasing the functionality and compactness of the optical element, and limiting the upper limit of the refractive index is advantageous in increasing the glass stability.

  The Abbe number νd of the optical glass of the present invention is 25 to 45. When correcting chromatic aberration in combination with a lens made of high dispersion glass, it is advantageous that the Abbe number νd is large. From this viewpoint, the preferable lower limit of the Abbe number νd is 26, the more preferable lower limit is 27, the still more preferable lower limit is 28, and the still more preferable lower limit is 29. On the other hand, relaxing the upper limit of the Abbe number νd works advantageously in maintaining and improving the glass stability. From this point of view, the preferred upper limit of the Abbe number νd is 43, the more preferred upper limit is 40, the still more preferred upper limit is 38, the still more preferred upper limit is 36, the still more preferred upper limit is 35, the still more preferred upper limit is 34, and the even more preferred upper limit is 33, An even more preferred upper limit is 32.

  The optical glass having a further increased refractive index is suitable as a material for optical elements suitable for downsizing and high-performance optical systems such as an imaging optical system and a projection optical system. In addition, even when lenses having the same focal length are manufactured, the absolute value of the curvature of the optical function surface of the lens can be reduced (the curve is relaxed), which is advantageous in terms of lens molding and processing. . On the other hand, by further increasing the refractive index of the optical glass, the thermal stability of the glass decreases or the coloring increases, that is, the light transmittance in the visible short wavelength region tends to decrease. Therefore, from the viewpoint of use and productivity, the optical glass of the present invention is roughly divided into a case where priority is given to further increasing the refractive index and a case where priority is given to improving thermal stability or reducing coloration, You can also use them properly.

In the optical glass of the present invention, when priority is given to further increasing the refractive index, the preferable lower limit of the refractive index nd is 1.966, the more preferable lower limit is 1.967, and the further preferable lower limit is 1.968. The preferred range of the Abbe number νd is 25 to 34, the more preferred range is 26 to 33, and the still more preferred range is 27 to 32. Even in the case where higher refractive index is prioritized, the refractive index nd is preferably 2.200 or less, more preferably 2.100 or less, from the viewpoint of maintaining glass stability. More preferably, it is 050 or less. Among the optical glasses of the present invention, those having a refractive index nd of 1.966 or more are referred to as optical glass A, and those having a refractive index nd of less than 1.966 are referred to as optical glass B.
In addition, the preferable range of Ti ⁴⁺ content in the case where the refractive index nd described above is 1.968 or more also applies to the preferable range of Ti ⁴⁺ content in the optical glass A.

  Since the optical glass of the present invention is a glass having a small partial dispersion ratio when the Abbe number νd is fixed, an optical element such as a lens made of the optical glass of the present invention is suitable for high-order chromatic aberration correction.

  Here, the partial dispersion ratio Pg, F is expressed as (ng−nF) / (nF−nc) using the refractive indexes ng, nF, and nc in the g-line, F-line, and c-line.

In order to provide an optical glass suitable for high-order chromatic aberration correction, in the optical glass of the present invention, it is preferable that the partial dispersion ratio Pg, F and the Abbe number νd satisfy the relationship of the following expression (1). Those satisfying the relationship of the formula (2) are more preferable, and those satisfying the relationship of the following formula (3) are more preferable.
Pg, F ≦ −0.0017 × νd + 0.660 (1)
Pg, F ≦ −0.0017 × νd + 0.655 (2)
Pg, F ≦ −0.0017 × νd + 0.650 (3)
Optical glass A and optical glass B, in particular optical glass B, are more preferred embodiments from the viewpoint of satisfying any of the above formulas (1) to (3).

Next, the light transmittance of the optical glass of the present invention will be described.
The optical glass of the present invention exhibits high light transmittance over a wide wavelength range in the visible range.
In a preferred embodiment of the optical glass of the present invention, λ70 exhibits a coloring degree of 470 nm or less. A more preferable range of λ70 is 465 nm or less, a further preferable range is 460 nm or less, a more preferable range is 455 nm or less, an even more preferable range is 450 nm or less, an even more preferable range is 445 nm or less, and an even more preferable range is 440 nm or less.

  Here, λ70 is a wavelength at which the light transmittance is 70% in the wavelength range of 280 to 700 nm. Here, the light transmittance means that a glass sample having parallel surfaces polished to a thickness of 10.0 ± 0.1 mm is used, and light is incident on the polished surface from a vertical direction. The obtained spectral transmittance, that is, Iout / Iin where Iin is the intensity of light incident on the sample and Iout is the intensity of light transmitted through the sample. The spectral transmittance includes light reflection loss on the sample surface. Moreover, the said grinding | polishing means that the surface roughness is smooth | blunted in the state small enough with respect to the wavelength of a measurement wavelength range.

  In a preferred embodiment of the optical glass of the present invention, the light transmittance exceeds 70% in the visible range longer than λ70. Similar to λ70, λ5 can also be defined as: λ5 is a wavelength at which the spectral transmittance is 5%.

  A preferable range of λ5 is 380 nm or less, a more preferable range is 375 nm or less, and a further preferable range is 365 nm or less.

As described above, the spectral transmittance is measured in the wavelength range of 280 to 700 nm. When the wavelength is increased from λ5, the light transmittance increases. When the wavelength reaches λ70, the spectral transmittance is as high as 70% or higher up to the wavelength of 700 nm. Keep the transmittance.
The optical glass A and the optical glass B, particularly the optical glass B, are more preferable from the viewpoint of obtaining the characteristics relating to the λ70 and λ5.

As will be described later, the lens made of the optical glass of the present invention can provide a compact and highly functional optical system with excellent chromatic aberration correction capability when combined with a lens made of ultra-low dispersion optical glass. Conventionally, a high refractive index and high dispersion glass lens has been used as a combination with an ultra low dispersion glass lens in a chromatic aberration correcting optical system. However, a high refractive index and high dispersion glass has a relatively large amount of TiO ₂ and Nb _2. A component having a high refractive index and high dispersion such as O ₅ , Bi ₂ O ₃ and WO ₃ is contained, and a sufficiently high light transmittance may not be obtained on the short wavelength side in the visible region. In a chromatic aberration correction optical system that combines a lens made of ultra-low dispersion glass and a lens made of high refractive index and high dispersion glass, the transmittance of the lens made of high refractive index and high dispersion glass with respect to light on the short wavelength side in the visible region, such as blue. Due to the decrease, the visible light transmittance of the entire optical system decreases. By using the lens made of the optical glass of the present invention instead of the high refractive index and high dispersion glass lens, the light transmittance in the visible region of the entire chromatic aberration correcting optical system is sufficiently secured.
From such a viewpoint, in the present invention, an optical glass in which λ5 is also in the above range is preferable.

(Glass transition temperature of optical glass)
The optical glass of the present invention is a glass suitable for forming a smooth optical functional surface by grinding and polishing. The suitability of cold working such as grinding and polishing, that is, cold workability is indirectly related to the glass transition temperature. A glass with a low glass transition temperature is more suitable for precision press molding than cold workability, whereas a glass with a high glass transition temperature is more suitable for cold work than precision press molding. Excellent. Therefore, also in the present invention, the glass transition temperature is preferably not lowered excessively, preferably higher than 630 ° C., more preferably 640 ° C. or higher, and further preferably 660 ° C. or higher. However, if the glass transition temperature is too high, the heating temperature at the time of reheating and softening the glass will increase, and the mold used for molding will deteriorate significantly, the annealing temperature will also become high, and the annealing furnace will Deterioration and wear are also significant. Accordingly, the glass transition temperature is preferably 750 ° C. or less, more preferably 740 ° C. or less, further preferably 730 ° C. or less, further preferably 725 ° C. or less, and 710 ° C. or less. It is even more preferable.

(Thermal stability of optical glass)
The liquidus temperature of the preferred embodiment of the optical glass of the present invention is 1220 ° C. or lower. Moreover, the preferable range of the liquidus temperature of the optical glass A is 1210 degreeC or less, and a more preferable range is 1200 degreeC or less. A preferable range of the liquidus temperature of the optical glass B is 1200 ° C. or less, and a more preferable range is 1190 ° C. or less. As described above, since the optical glass of the present invention is a high-refractive index low-dispersion glass and has excellent thermal stability, it is possible to stably produce high-quality optical glass. In addition, while preventing devitrification, the melting temperature can be lowered and the melting of platinum or platinum alloy constituting the crucible into the glass can be suppressed. It can also be suppressed and prevented.

(Optical glass manufacturing method)
Next, the manufacturing method of the optical glass of this invention is demonstrated. For example, a powdery compound raw material or cullet raw material is weighed and prepared in accordance with the target glass composition, supplied into a platinum alloy melting vessel, and then heated and melted. After the above raw materials are completely melted and vitrified, the temperature of the molten glass is raised to clarify. The clarified molten glass is homogenized by stirring with a stirrer, and continuously supplied to and discharged from a glass outlet pipe, rapidly cooled and solidified to obtain a glass molded body.
In addition, it is desirable that the melting temperature of the optical glass be in the range of 1250 to 1400 ° C. in order to obtain a glass that is homogeneous, low-colored, and stable in various properties including optical properties.
Next, the glass gob for press molding according to the present invention will be described.

[Glass bump for press molding]
The glass gob for press molding of the present invention is characterized by comprising the above-described optical glass of the present invention. The shape of the gob is set to be easy to press according to the shape of the target press-formed product. The mass of the gob is also set according to the press-formed product. In the present invention, since glass having excellent stability is used, even if it is reheated, softened and press-molded, the glass is hardly devitrified, and a high-quality molded product can be stably produced. .
The production example of the glass gob for press molding is as follows.

In the first production example, the molten glass flowing out from the pipe is continuously cast into a mold horizontally disposed below the outflow pipe, and formed into a plate shape having a certain thickness. The molded glass is continuously pulled out in the horizontal direction from an opening provided on the side surface of the mold. The sheet glass molded body is pulled out by a belt conveyor. A glass molded body having a predetermined thickness and plate width can be obtained by pulling out the glass molded body so that the plate thickness of the glass molded body is constant at a constant belt conveyor drawing speed. The glass molded body is conveyed into an annealing furnace by a belt conveyor and gradually cooled. The slowly cooled glass molded body is cut or cleaved in the plate thickness direction and polished or barrel-polished to form a glass gob for press molding.

  In the second production example, molten glass is cast into a cylindrical mold instead of the above mold to form a columnar glass molded body. The glass molded body molded in the mold is drawn vertically downward from the opening at the bottom of the mold at a constant speed. The drawing speed may be set so that the molten glass liquid level in the mold becomes constant. After slowly cooling the glass molded body, it is cut or cleaved, and subjected to polishing or barrel polishing to obtain a glass gob for press molding.

  In the third manufacturing example, a molding machine in which a plurality of molding dies are arranged at equal intervals on the circumference of a circular turntable below the outflow pipe is installed below the outflow pipe, and the turntable is index-rotated. The molten glass is supplied as a position where the molten glass is supplied to the mold (referred to as a cast position), and the supplied molten glass is formed into a glass molded body, and then is different from the cast position. The glass molded body is taken out from the stop position (takeout position) of the mold. The stop position as the take-out position may be determined in consideration of the rotation speed of the turntable, the cooling speed of the glass, and the like. The molten glass is supplied to the mold at the casting position by dropping molten glass from the glass outlet of the outflow pipe and receiving the glass droplets at the above-mentioned mold, and by bringing the molding mold retained at the casting position closer to the glass outlet. Supports the lower end of the flowing molten glass flow, creates a constriction in the middle of the glass flow, and rapidly drops the mold in the vertical direction at a predetermined timing to separate the molten glass below the constriction and receive it on the mold It can be performed by a method, a method in which the flowing molten glass flow is cut with a cutting blade, and the separated molten glass lump is received by a mold that is retained at the casting position.

  A known method may be used to form the glass on the mold. Above all, when gas is blown upward from the mold and an upward wind pressure is applied to the glass lump to form the glass while it floats, the surface of the glass mold is wrinkled, or the glass mold can be contacted with the mold by contact with the mold. It is possible to prevent cracks from occurring.

  The shape of the glass molded body is spherical, spheroid, and has one rotation target axis depending on the selection of the mold shape and the gas ejection method, and two surfaces facing the axis direction of the rotation target axis. Can be formed into a shape that is convex outward. These shapes are suitable for a glass gob for press molding an optical element such as a lens or an optical element blank. The glass molded body thus obtained can be used as it is, or the surface can be polished or barrel-polished to form a glass gob for press molding.

[Optical element]
Next, the optical element of the present invention will be described.
The optical element of the present invention is characterized by comprising the above-described optical glass of the present invention. The optical element of the present invention has high refractive index and low dispersion characteristics, and the content of expensive components such as Ta and Ge is suppressed to a relatively small amount or zero. Optical elements such as various high lenses and prisms can be provided.

  Examples of the lens include various lenses such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a planoconvex lens, and a planoconcave lens having a spherical or aspheric lens surface.

  Such a lens can correct chromatic aberration when combined with a lens made of low dispersion glass, and is suitable as a lens for correcting chromatic aberration. It is also an effective lens for making the optical system compact.

In addition, since the prism has a high refractive index, a compact optical system with a wide angle of view can be realized by incorporating the prism into the imaging optical system and bending the optical path in a desired direction.
Note that a film for controlling light transmittance such as an antireflection film may be provided on the optical functional surface of the optical element of the present invention.

[Method for manufacturing optical element blank]
Next, the manufacturing method of the optical element blank of this invention is demonstrated.
The optical element blank manufacturing method of the present invention has the following two modes.

(Method for manufacturing first optical element blank)
The first optical element blank manufacturing method of the present invention is a method of manufacturing an optical element blank that is finished into an optical element by grinding and polishing, and heating and softening the press molding glass gob of the present invention described above for press molding. It is characterized by.

  The optical element blank is a glass molded body having a shape approximate to the shape of the optical element obtained by adding a processing margin to be removed by grinding and polishing to the shape of the target optical element.

  In producing an optical element blank, a press mold having a molding surface having a shape obtained by inverting the shape of the blank is prepared. The press mold is composed of mold parts including an upper mold, a lower mold, and, if necessary, a barrel mold, and the upper and lower mold molding surfaces, or the barrel mold molding surface when the barrel mold is used, have the aforementioned shape.

  Next, a powder mold release agent such as boron nitride is uniformly applied to the surface of the glass gob for press molding, heated and softened, introduced into the preheated lower mold, and pressed with the upper mold facing the lower mold. Then, it is formed into an optical element blank.

  Next, the optical element blank is released, removed from the press mold, and annealed. By this annealing treatment, the distortion inside the glass is reduced so that the optical characteristics such as the refractive index become a desired value.

  The glass gob heating conditions, press molding conditions, materials used for the press mold, and the like may be applied. The above steps can be performed in the atmosphere.

(Manufacturing method of the second optical element blank)
The manufacturing method of the 2nd optical element blank of this invention is a manufacturing method of the optical element blank finished to an optical element by grinding and grinding | polishing, melt | dissolves a glass raw material, press-molds the obtained molten glass, and described above An optical element blank made of the optical glass of the invention is produced.

  A press mold is composed of mold parts including an upper mold, a lower mold, and, if necessary, a barrel mold. As described above, the molding surface of the press mold is processed into a shape obtained by inverting the surface shape of the optical element blank.

  A powder mold release agent such as boron nitride is uniformly applied on the lower mold surface, and the molten glass melted in accordance with the optical glass manufacturing method described above flows out onto the lower mold surface, and the molten glass on the lower mold. When the amount reaches a desired amount, the molten glass stream is cut with a cutting blade called a shear. After obtaining a molten glass lump on the lower mold in this manner, the lower mold is moved together with the molten glass lump to a position where the upper mold waits upward, and the glass is pressed with the upper mold and the lower mold to form an optical element blank. .

  Next, the optical element blank is released, removed from the press mold, and annealed. By this annealing treatment, the distortion inside the glass is reduced so that the optical characteristics such as the refractive index become a desired value.

The glass gob heating conditions, press molding conditions, materials used for the press mold, and the like may be applied. The above steps can be performed in the atmosphere.
Next, the manufacturing method of the optical element of this invention is demonstrated.

[Method of manufacturing optical element]
The optical element manufacturing method of the present invention is characterized in that the optical element blank produced by the above-described method of the present invention is ground and polished. Known methods can be applied to the grinding and polishing.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples. The optical glass of the present invention can be obtained by applying the above-described method for adjusting the content of each glass component with reference to the glass of this example.

Example 1
First, oxide glass No. 1 having the composition (expressed as cation%) shown in Table 1-1 to Table 1-4. 1 to 36 is obtained, using nitrate, sulfate, hydroxide, oxide, boric acid, etc. as raw materials, each raw material powder is weighed and mixed well to prepare a mixed raw material, and this mixed raw material is made of platinum It put in the crucible, and it heated and melted at 1400 degreeC, it clarified and stirred and it was made into the homogeneous molten glass. The molten glass was poured into a preheated mold and rapidly cooled, held at a temperature in the vicinity of the glass transition temperature for 2 hours, and then slowly cooled to obtain oxide glass no. Each optical glass of 1-36 was obtained. No crystal precipitation was observed in any glass.

In addition, oxide glass No. The total amount of anionic components 1 to 36 is O ²⁻ . Tables 2-1 to 2-3 show oxide glass Nos. Compositions represented by 1 to 36% by mass and Tables 3-1 to 3-3 are compositions represented by mol%.

The characteristic of each glass was measured by the method shown below. The measurement results are shown in Table 1-5.
(1) Refractive index nd and Abbe number νd
It measured about the optical glass cooled with the temperature-fall rate of 30 degreeC per hour.
(2) Partial dispersion ratio Pg, F
Refractive indexes ng, nF and nc were measured for the optical glass cooled at a temperature drop rate of 30 ° C. per hour and calculated from these values.
(3) Glass transition temperature Tg
Using a thermomechanical analyzer, the measurement was performed under the condition of a heating rate of 4 ° C./min.
(4) Liquidus temperature The glass was placed in a furnace heated to a predetermined temperature and held for 2 hours. After cooling, the inside of the glass was observed with a 100-fold optical microscope, and the liquidus temperature was determined from the presence or absence of crystals.
(5) Specific gravity It measured by Archimedes method.
(6) λ70, λ5
A glass sample having parallel surfaces polished to a thickness of 10.0 ± 0.1 mm is used, and a spectrophotometer is used to inject light having an intensity Iin from a direction perpendicular to the polished surface. The light transmittance Iout / Iin was calculated by measuring the intensity Iout of the light transmitted through the light. The wavelength at which the light transmittance was 70% was λ70, and the wavelength at which the light transmittance was 5% was λ5.

(Example 2)
Next, a glass gob for press molding made of each optical glass of Example 1 was produced as follows.
First, glass raw materials were prepared so as to obtain the above glasses, put into a platinum crucible, heated, melted, clarified and stirred to obtain a homogeneous molten glass. Next, the molten glass was flown out from the outflow pipe at a constant flow rate and cast into a mold placed horizontally below the outflow pipe to form a glass plate having a constant thickness. The formed glass plate was continuously pulled out from the opening provided on the side surface of the mold in the horizontal direction, conveyed to the annealing furnace by a belt conveyor, and gradually cooled.

  The slowly cooled glass plate was cut or cleaved to produce glass pieces, and these glass pieces were barrel-polished to form glass gob for press molding.

  A cylindrical mold is disposed below the outflow pipe, molten glass is cast into the mold to form a cylindrical glass, and is drawn vertically downward from the opening at the bottom of the mold at a constant speed. Glass pieces can be obtained by cooling, cutting or cleaving to make glass pieces, and barrel-polishing these glass pieces.

(Example 3)
In the same manner as in Example 2, after the molten glass flows out from the outflow pipe and receives the lower end of the molten glass flowing out from the mold, the mold is rapidly lowered, the molten glass flow is cut by the surface tension, and the desired shape is placed on the mold. An amount of molten glass ingot was obtained. Then, gas was blown out from the mold, an upward wind pressure was applied to the glass, and the glass was molded into a glass lump while being lifted, taken out from the mold and annealed. The glass lump was then barrel-polished to form a glass gob for press molding.

Example 4
After uniformly applying a release agent composed of boron nitride powder to the entire surface of each press-molding glass gob obtained in Example 3, the gob was heated, softened and press-molded to form a concave meniscus lens, a convex meniscus lens, Various lenses such as a biconvex lens, a biconcave lens, a planoconvex lens, and a planoconcave lens, and a prism blank were prepared.

(Example 5)
In the same manner as in Example 2, a molten glass was prepared, and the molten glass was supplied to the lower mold forming surface uniformly coated with the release agent of boron nitride powder. When the amount of molten glass on the lower mold reached a desired amount, the molten glass was melted. The glass stream was cut with a cutting blade.

  The molten glass block thus obtained on the lower mold was pressed with the upper mold and the lower mold, and a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, a plano-concave lens, etc., and a prism blank were produced. .

(Example 6)
Each blank produced in Examples 4 and 5 was annealed. Annealing reduces the internal strain of the glass so that the optical properties such as the refractive index become a desired value.
Next, each blank was ground and polished to prepare various lenses and prisms such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a planoconvex lens, and a planoconcave lens. The surface of the obtained optical element may be coated with an antireflection film.

(Example 7)
A glass plate and a columnar glass were produced in the same manner as in Example 2, and the obtained glass molded body was annealed to reduce internal strain and to make optical characteristics such as refractive index have desired values.
Next, these glass moldings were cut, ground, and polished to prepare concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, planoconvex lenses, planoconcave lenses, and other lenses, and prism blanks. An antireflection film may be coated on the surface of the obtained optical element.

  The present invention is an optical glass that can be stably supplied and has high refractive index and low dispersion having excellent glass stability, and is suitable for a glass gob for press molding, an optical element blank, and an optical element.

Claims (5)

Oxide glass, expressed as cation%,
Si ⁴⁺ 1 ~30%,
B ³⁺ 13 to 45 %,
Li ⁺ , Na ⁺ and K ⁺ in total less than 5%,
Less than 5% in total Mg ²⁺ , Ca ²⁺ and Sr ²⁺
Ba ²⁺ 0-8%,
Zn ²⁺ 0.1~ 12%,
La ³⁺ 10~ 40%,
Gd ³⁺ 0-20%,
Y ³⁺ 0.25-15%,
Yb ³⁺ 0-10%,
Zr ⁴⁺ 1 ~20%,
Ti ⁴⁺ 1 ~22%,
Nb ⁵⁺ 0.1-20 %,
Ta ⁵⁺ 0-8%,
W ⁶⁺ 0-5%,
Ge ⁴⁺ 0-8%,
Bi ³⁺ 0-10%,
Al ³⁺ 0-10%,
Wherein the content of the cation ratio of Si ⁴⁺ / B ³⁺ is less than 1.0 of Si ⁴⁺ to the content of B ^3+, the total content of in terms of oxide Nb ₂ O ₅ and Ta ₂ O ₅ The amount is less than 14% by weight,
An optical glass having a refractive index nd of 1.92 to 2.2, an Abbe number νd of 25 to 45, and a glass transition temperature Tg of 630 ° C. or higher. The optical glass according to claim 1, wherein the coloring degree λ70 is less than 470 nm. The optical glass according to claim 1 or 2 , wherein the partial dispersion ratio Pg, F and the Abbe number νd satisfy the relationship of the following formula (1).
Pg, F ≦ −0.0017 × νd + 0.660 (1) A glass gob for press molding, comprising the optical glass according to any one of claims 1 to 3 . It consists of the optical glass of any one of Claims 1-3 , The optical element characterized by the above-mentioned.