JP6033486B2 - Optical glass, preform material and optical element - Google Patents

Description

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

  In recent years, digitization and high definition of devices using optical systems have been rapidly progressing, and various optical devices such as photographing devices such as digital cameras and video cameras, and image reproduction (projection) devices such as projectors and projection televisions. In this field, there is an increasing demand to reduce the number of optical elements such as lenses and prisms used in the optical system, and to reduce the weight and size of the entire optical system.

Among optical glasses for producing optical elements, in particular, it has a refractive index (n _d ) of 1.75 or more and an Abbe number of 30 or more and 50 or less (which can reduce the weight and size of the entire optical system). There is a great demand for high refractive index, low dispersion glass capable of precision mold pressing with ν _d ). As such a high refractive index and low dispersion glass, glass compositions represented by Patent Documents 1 and 2 are known.

JP 2001-348244 A JP 2008-001551 A

  The lenses used in the optical system include a spherical lens and an aspheric lens. If an aspheric lens is used, the number of optical elements can be reduced. In addition, various optical elements other than lenses are known which have a complicatedly shaped surface. However, in order to obtain an aspherical surface or a complicatedly shaped surface by conventional grinding and polishing processes, a high-cost and complicated work process is required. Therefore, a method of obtaining a shape of an optical element by directly press-molding a preform material obtained from a gob or a glass block with an ultra-precision processed mold, that is, a method of precision mold press molding is currently mainstream.

  In addition to the method of precision mold press molding a preform material, a glass molded body obtained by reheating and molding (reheat press molding) a gob or glass block formed from a glass material is ground and polished. Methods are also known.

  As a manufacturing method of a preform material used for such precision mold press molding and reheat press molding, a method of directly manufacturing from a molten glass by a dropping method, a reheat press of a glass block, or a grinding process into a ball shape is obtained. There is a method of grinding and polishing processed products. In any method, in order to obtain an optical element by forming a molten glass into a desired shape, it is required to reduce devitrification of the formed glass.

  In addition, in order to reduce the material cost of the optical glass, it is desirable that the raw material costs of the components constituting the optical glass be as low as possible. Moreover, in order to reduce the manufacturing cost of optical glass, it is desired that the raw material has high meltability, that is, it is melted at a lower temperature. However, it is difficult to say that the glass compositions described in Patent Documents 1 and 2 sufficiently satisfy these various requirements.

The present invention has been made in view of the above problems, and its object is to provide resistance to devitrification while the refractive index (n _d ) and Abbe number (ν _d ) are within the desired ranges. It is to obtain a preform material having a high price at a lower cost.

In order to solve the above-mentioned problems, the present inventors have conducted extensive test studies. As a result, in a glass containing a B ₂ O ₃ component and a La ₂ O ₃ component, the TiO ₂ component, the WO ₃ component, and the Nb ₂ O It has been found that by containing at least one of the _five components as an essential component, a desired optical constant can be obtained even if the Ta ₂ O ₅ component, which is expensive and has poor meltability, is reduced. It came to do. Specifically, the present invention provides the following.

(1) the glass the total amount of substance of the oxide composition in terms of, 10.0 to 50.0% of _B 2 _{O 3} component in mole% and the _La 2 _{O 3} component contained 5.0 to 30.0% An optical glass having a molar sum (TiO ₂ + WO ₃ + Nb ₂ O ₅ ) of 0.1 to 30.0% with respect to the total amount of the glass having an oxide equivalent composition.

(2) The optical glass according to (1), wherein the content of the WO ₃ component is 20.0% or less in terms of mol% with respect to the total amount of the glass having an oxide conversion composition.

(3) The optical glass according to (1), wherein the content of the WO ₃ component is less than 7.0% in terms of mol% with respect to the total amount of the glass having an oxide conversion composition.

(4) TiO ₂ component 0 to 20.0% and / or Nb ₂ O ₅ component 0 to 20.0% in mol% with respect to the total amount of glass in the oxide conversion composition
The optical glass according to any one of (1) to (3), further comprising:

(5) The optical glass according to (4), wherein a molar sum (TiO ₂ + Nb ₂ O ₅ ) with respect to the total amount of glass having an oxide conversion composition is 2.0% or more and 30.0% or less.

(6) The optical glass according to any one of (1) to (5), wherein the molar ratio WO ₃ / (TiO ₂ + Nb ₂ O ₅ + WO ₃ ) of the oxide equivalent composition is 0.600 or less.

(7) as oxide with respect to the glass the total amount of substance of the composition, the optical glass according to any one of the Li ₂ O content component is not more than 20.0% by mole% (1) to (6).

(8) The optical glass according to (7), wherein the content of the Li ₂ O component is 0.1% or more in terms of mol% with respect to the total amount of the glass having an oxide conversion composition.

(9) Gd ₂ O ₃ component 0 to 30.0% and / or Y ₂ O ₃ component 0 to 10.0% and / or Yb ₂ O in mol% with respect to the total amount of glass in the oxide equivalent composition ₃ components 0 to 10.0% and / or Lu ₂ O ₃ components 0 to 10.0%
The optical glass according to any one of (1) to (8), further comprising:

(10) The molar sum of the Ln ₂ O ₃ component (wherein Ln is one or more selected from the group consisting of La, Gd, Y, Yb, and Lu) with respect to the total amount of glass in the oxide equivalent composition is 10. The optical glass according to any one of (1) to (9), which is 0% or more and 40.0% or less.

(11) The optical glass according to any one of (1) to (10), containing two or more components among the Ln ₂ O ₃ components.

(12) The optical glass according to any one of (1) to (11), wherein the content of the Ta ₂ O ₅ component is 20.0% or less in terms of mol% with respect to the total amount of the glass having an oxide equivalent composition.

(13) The optical glass according to (12), wherein the molar ratio Ta ₂ O ₅ / WO _{3 of the} oxide equivalent composition is 1.0 or more and 10.0 or less.

(14) The optical glass according to any one of (1) to (13), wherein the content of the SiO ₂ component is 25.0% or less in terms of mol% with respect to the total amount of the glass having an oxide conversion composition.

(15) The optical glass according to (14), wherein the content of SiO ₂ component is 19.0% or less in terms of mol% with respect to the total amount of the glass having an oxide conversion composition.

(16) Na ₂ O component 0 to 15.0% and / or K ₂ O component 0 to 10.0% in mol% with respect to the total amount of glass in the oxide conversion composition
The optical glass according to any one of (1) to (15), further comprising:

(17) The molar sum of the Rn ₂ O component (wherein Rn is one or more selected from the group consisting of Li, Na, and K) with respect to the total amount of glass in an oxide equivalent composition is 20.0% or less. (16) The optical glass as described.

(18) 0 to 10.0% of MgO component and / or 0 to 10.0% of CaO component and / or 0 to 10.0% of SrO component and mol% with respect to the total amount of glass in the oxide conversion composition / Or BaO component 0 to 10.0%
The optical glass according to any one of (1) to (17), further comprising:

  (19) The molar sum of the RO component (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, and Ba) with respect to the total amount of glass in the oxide equivalent composition is 11.0% or less. (18) The optical glass as described.

(20) GeO ₂ component 0 to 10.0% and / or P ₂ O ₅ component 0 to 10.0% and / or ZrO ₂ component 15.0% and / or ZnO component 0 to 50.0% and / or Bi ₂ O ₃ component 0 to 15.0% and / or TeO ₂ component 0 to 15.0% and / or Al ₂ O ₃ component 0 15.0% and / or _Ga 2 _{O 3} component from 0 to 15.0% and / or _Sb 2 _{O 3} component from 0 to 1.0%
Each component of
Any one of (1) to (19), wherein the content of F as a substitute for a part or all of one or more oxides of each metal element is 0 to 6.0%. Optical glass.

(21) The optical glass according to any one of (1) to (20), which has a refractive index (n _d ) of 1.75 or more and 1.95 or less and an Abbe number (ν _d ) of 30 or more and 50 or less.

  (22) The optical glass according to any one of (1) to (21), which has a glass transition point (Tg) of 680 ° C. or lower.

  (23) The optical glass according to any one of (1) to (22), which has a liquidus temperature of 1250 ° C. or lower.

  (24) A preform made of the optical glass according to any one of (1) to (23).

  (25) An optical element produced by press-molding the preform material according to (24).

  (26) An optical element having the optical glass according to any one of (1) to (23) as a base material.

  (27) An optical apparatus comprising the optical element according to any one of (25) or (26).

According to the present invention, the glass containing B ₂ O ₃ component and La ₂ O ₃ component contains one or more selected from the group consisting of TiO ₂ component, WO ₃ component and Nb ₂ O ₅ component By doing so, it becomes possible to obtain a desired optical constant with a cheaper component. Therefore, an optical glass capable of obtaining a preform material having high devitrification resistance while the refractive index (n _d ) and the Abbe number (ν _d ) are within the desired ranges can be obtained at low cost. .

In the optical glass of the present invention, the B ₂ O ₃ component is 10.0 to 50.0% and the La ₂ O ₃ component is 5.0 to 30. The molar sum (TiO ₂ + WO ₃ + Nb ₂ O ₅ ) is 0.1 to 30.0% with respect to the total amount of glass in the oxide equivalent composition. By containing at least one selected from the group consisting of TiO ₂ component, WO ₃ component, and Nb ₂ O ₅ component, the desired optics can be obtained even if Ta ₂ O ₅ component that is expensive and has poor meltability is reduced. A constant is obtained. At the same time, based on the B ₂ O ₃ component and the La ₂ O ₃ component, it has a refractive index (n _d ) of 1.75 or more and 1.95 or less and an Abbe number (ν _d ) of 30 or more and 50 or less. However, the liquidus temperature tends to be low. Therefore, an optical glass capable of obtaining a preform material having high devitrification resistance while the refractive index (n _d ) and the Abbe number (ν _d ) are within the desired ranges can be obtained at low cost. .

The optical glass of the present invention contains one or more selected from the group consisting of TiO ₂ component, WO ₃ component and Nb ₂ O ₅ component as essential components. Of these TiO ₂ component, WO ₃ component and Nb ₂ O ₅ component, a glass containing at least a TiO ₂ component and / or a Nb ₂ O ₅ component will be described as a first optical glass. Moreover, glass containing at least the WO ₃ component among the TiO ₂ component, the WO ₃ component, and the Nb ₂ O ₅ component will be described as the second optical glass. The optical glass of the present invention may contain both a TiO ₂ component and / or an Nb ₂ O ₅ component and a WO ₃ component.

  Hereinafter, embodiments of the optical glass of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. In addition, although description may be abbreviate | omitted suitably about the location where description overlaps, the meaning of invention is not limited.

[Glass component]
The composition range of each component constituting the optical glass of the present invention is described below. In the present specification, unless otherwise specified, the content of each component is expressed in mol% with respect to the total amount of glass in the oxide conversion composition. Here, the “oxide equivalent composition” is based on the assumption that the oxide, composite salt, metal fluoride, etc. used as the raw material of the glass component of the present invention are all decomposed and changed into oxides during melting. It is the composition which described each component contained in glass by making the total amount of substances of a production | generation oxide into 100 mol%.

<About essential and optional components>
The B ₂ O ₃ component is an essential component as a glass-forming oxide in the optical glass of the present invention containing a large amount of rare earth oxides. In particular, by making the content of the B ₂ O ₃ component 10.0% or more, the devitrification resistance of the glass can be increased and the dispersion of the glass can be reduced. Therefore, the content of the B ₂ O ₃ component with respect to the total amount of glass in the oxide conversion composition is preferably 10.0%, more preferably 15.0%, and most preferably 20.0%. On the other hand, by setting the content of the B ₂ O ₃ component to 50.0% or less, it is possible to easily obtain a larger refractive index and suppress deterioration of chemical durability. Therefore, the upper limit of the content of the B ₂ O ₃ component with respect to the total amount of glass in the oxide conversion composition is preferably 50.0%, more preferably 48.0%, and most preferably 46.0%. The B ₂ O ₃ component can be contained in the glass using, for example, H ₃ BO ₃ , Na ₂ B ₄ O ₇ , Na ₂ B ₄ O ₇ .10H ₂ O, BPO ₄ or the like as a raw material.

The La ₂ O ₃ component is a component that increases the refractive index of the glass and decreases the dispersion of the glass to increase the Abbe number of the glass. In particular, by setting the content of _La 2 _{O 3} component in more than 5.0%, it is possible to increase the refractive index of the glass. Therefore, the content of the La ₂ O ₃ component with respect to the total amount of glass in the oxide conversion composition is preferably 5.0%, more preferably 8.0%, and most preferably 10.0%. On the other hand, devitrification can be reduced by increasing the stability of the glass by setting the content of the La ₂ O ₃ component to 30.0% or less. Accordingly, the La ₂ O ₃ component content is preferably 30.0%, more preferably 25.0%, even more preferably 20.0%, and most preferably 18.0% with respect to the total amount of glass in the oxide equivalent composition. The upper limit is 0%. The La ₂ O ₃ component can be contained in the glass using, for example, La ₂ O ₃ , La (NO ₃ ) ₃ .XH ₂ O (X is an arbitrary integer) or the like as a raw material.

In the optical glass of the present invention, it is preferable that the molar sum of one or more selected from the group consisting of TiO ₂ component, WO ₃ component and Nb ₂ O ₅ component is 0.1% or more and 30.0% or less. In particular, when the molar sum is 0.1% or more, a desired optical constant can be obtained even if the Ta ₂ O ₅ component is reduced. Therefore, an optical glass having desired optical characteristics can be produced at a lower cost. On the other hand, when the molar sum is 30.0% or less, an increase in the liquidus temperature due to excessive inclusion of these components can be suppressed, so that the optical glass can be produced more stably. Therefore, the molar sum of these components with respect to the total amount of glass in the oxide conversion composition is preferably 0.1%, more preferably 1.0%, and most preferably 1.5%. On the other hand, the molar sum of these components with respect to the total amount of glass in the oxide conversion composition is preferably 30.0%, more preferably 28.0%, still more preferably 26.0%, and most preferably 11 Less than 0%. In particular, in the second optical glass, from the viewpoint of further increasing the refractive index and resistance to devitrification, the molar sum of these components is preferably 20.0%, more preferably 18.0%, and even more preferably 15.0%. May be the upper limit.

The WO ₃ component is a component that increases the refractive index of the glass and improves the devitrification resistance of the glass. On the other hand, by setting the content of the WO ₃ component to 20.0% or less, it is possible to form a glass having high refractive index and devitrification resistance while suppressing high dispersion. Further, by making the content of the WO ₃ component 20.0% or less, it is possible to make it difficult to lower the transmittance particularly in the visible-short wavelength region (less than 500 nm). Accordingly, the content of the WO ₃ component with respect to the total amount of glass in the oxide conversion composition is preferably 20.0%, more preferably 15.0%, still more preferably 10.0%, and most preferably 7%. Less than 0%. Particularly in the first optical glass, from the viewpoint of being a component that is difficult to increase the refractive index of the glass, the content of the WO ₃ component is preferably 4.0%, more preferably 3.0% as the upper limit, Most preferably, it may be less than 1.0%. The optical glass of the present invention, it is possible to obtain a glass having desired optical constants and devitrification resistance even without containing WO ₃ components, by containing a WO ₃ components, high refractive While obtaining the rate, the glass transition point can be further lowered. Therefore, the content of the WO ₃ component is preferably 0.1%, more preferably 0.5%, and even more preferably 1.0% with respect to the total amount of glass in the oxide conversion composition, particularly in the second optical glass. Most preferably, the lower limit is 1.5%. The WO ₃ component can be contained in the glass using, for example, WO ₃ as a raw material.

The TiO ₂ component is a component that adjusts the refractive index and Abbe number of the glass to be high and improves devitrification resistance, and is an optional component in the optical glass of the present invention. However, when there is too much TiO ₂ , the devitrification resistance is adversely affected, and the transmittance of the glass at a visible short wavelength (500 nm or less) is also deteriorated. Therefore, the upper limit of the content of the TiO ₂ component with respect to the total amount of glass in the oxide conversion composition is preferably 20.0%, more preferably 15.0%, and most preferably 12.0%. Although glass having the desired properties without containing TiO ₂ component is obtained, by containing a TiO ₂ component, without reducing the stability of the glass, it is possible to obtain a high refractive index. Moreover, stability can also be improved by lowering the liquidus temperature of the glass. Therefore, particularly in the first optical glass, the content of the TiO ₂ component is preferably 0.1%, more preferably 3.0%, and even more preferably 5.0% with respect to the total amount of glass in the oxide conversion composition. Is the lower limit, and may be more preferably more than 8.0%. TiO ₂ component may be contained in the glass by using as the starting material for example TiO ₂ or the like.

Nb ₂ O ₅ component is a component to increase adjusting the refractive index and dispersion of the glass, an optional component of the optical glass of the present invention. In particular, by reducing the content of the Nb ₂ O ₅ component to 20.0% or less, deterioration of the devitrification resistance of the glass due to the excessive content of the Nb ₂ O ₅ component is suppressed, and the glass transmits visible light. Reduction in rate can be suppressed. Therefore, the content of the Nb ₂ O ₅ component is preferably 20.0%, more preferably 15.0%, still more preferably 10.0%, and most preferably 7.7% with respect to the total amount of glass in the oxide equivalent composition. The upper limit is 0%. Although glass having the desired properties without containing Nb ₂ O ₅ component is obtained, by containing Nb ₂ O ₅ component, without reducing the stability of the glass, to obtain a high refractive index It becomes possible. Moreover, stability can also be improved by lowering the liquidus temperature of the glass. Therefore, the content of the Nb ₂ O ₅ component with respect to the total amount of the glass having an oxide conversion composition, particularly in the first optical glass, is preferably 0.1% as a lower limit, more preferably more than 2.0%. More preferably, the lower limit is 5.0%, and most preferably more than 8.0%. The Nb ₂ O ₅ component can be contained in the glass using, for example, Nb ₂ O ₅ as a raw material.

In the first optical glass of the present invention, the sum of the contents of the TiO ₂ component and the Nb ₂ O ₅ component is preferably 2.0% or more and 30.0% or less. In particular, by making this sum 2.0% or more, it becomes possible to obtain a high refractive index while lowering the liquidus temperature of the glass. Therefore, the molar sum (TiO ₂ + Nb ₂ O ₅ ) of the oxide equivalent composition in the first optical glass is preferably 2.0%, more preferably 5.0%, and even more preferably 8.0%. And On the other hand, by making this sum 30.0% or less, deterioration of the devitrification resistance of the glass due to excessive inclusion of these components can be suppressed. Therefore, the molar sum (TiO ₂ + Nb ₂ O ₅ ) with respect to the total amount of glass in the oxide conversion composition is preferably 30.0%, more preferably 25.0%, and most preferably 20.0%. .

The first optical glass of the present invention is preferably TiO ₂ component, _Nb 2 _{O 5} component and a ratio of the WO ₃ content components to the sum of WO ₃ component is 0.600 or less. By reducing this ratio, it becomes easy to obtain a glass having a desired refractive index and Abbe number because the desired Abbe number of the glass is secured and the refractive index is easily increased. Moreover, since the total required amount of the TiO ₂ component, Nb ₂ O ₅ component and WO ₃ component having the effect of increasing both the refractive index and dispersion of the glass is reduced, the liquid phase temperature is increased due to the excessive content thereof. That is, devitrification can be reduced. Therefore, the molar ratio WO ₃ / (TiO ₂ + Nb ₂ O ₅ + WO ₃ ) of the oxide equivalent composition in the first optical glass is preferably 0.600, more preferably 0.500, and most preferably 0.370. Is the upper limit. On the other hand, the lower limit of the molar ratio WO ₃ / (TiO ₂ + Nb ₂ O ₅ + WO ₃ ) in the oxide equivalent composition may be zero.

The Li ₂ O component is a component that lowers the glass transition point. In particular, by setting the content of the Li ₂ O component to 20.0% or less, the liquidus temperature of the glass can be lowered to reduce devitrification. Therefore, the upper limit of the content of the Li ₂ O component with respect to the total amount of glass in the oxide conversion composition is preferably 20.0%, more preferably 15.0%, and most preferably 10.0%. Although the glass is obtained having the desired properties without containing Li 2 _O component, by containing Li 2 _O component, since the effect of lowering the glass transition temperature increases, easy optical glass perform press molding Can be easily obtained. Therefore, the content of the Li ₂ O component with respect to the total glass material amount of the oxide conversion composition is preferably 0.1%, more preferably 0.3%, and most preferably 0.5%.

The Gd ₂ O ₃ component is a component that increases the refractive index of the glass and increases the Abbe number, and is an optional component in the optical glass of the present invention. In particular, by setting the content of the Gd ₂ O ₃ component to 30.0% or less, it is easy to obtain a glass having a desired optical constant, and the glass transition point (Tg) due to excessive inclusion of the Gd ₂ O ₃ component. Can be suppressed, and the devitrification resistance of the glass can be increased. Therefore, the Gd ₂ O ₃ component content is preferably 30.0%, more preferably 20.0%, and most preferably 10.0% with respect to the total amount of glass in the oxide equivalent composition. Incidentally, in the case is not disadvantageous in the art without containing _Gd 2 _{O 3} component, by replacing a part of _La 2 _{O 3} component _Gd 2 _{O 3} component, not containing _Gd 2 _{O 3} component In comparison, the liquidus temperature of the glass may be lowered, and the devitrification resistance may be further improved. Therefore, the content of the Gd ₂ O ₃ component with respect to the total amount of glass in the oxide conversion composition is preferably more than 0%, more preferably 2.0% as the lower limit, and even more preferably more than 5.0%. To do. The Gd ₂ O ₃ component can be contained in the glass using, for example, Gd ₂ O ₃ , GdF ₃ or the like as a raw material.

The Y ₂ O ₃ component, the Yb ₂ O ₃ component, and the Lu ₂ O ₃ component are components that increase the refractive index of the glass and reduce the dispersion, and are optional components in the optical glass of the present invention. In particular, the desired optical constant of the glass can be easily obtained by reducing the content of each of the Y ₂ O ₃ component, the Yb ₂ O ₃ component and / or the Lu ₂ O ₃ component to 10.0% or less. The devitrification resistance can be improved. Therefore, the content of each component of Y ₂ O ₃ , Yb ₂ O _3, and Lu ₂ O ₃ with respect to the total amount of glass in the oxide conversion composition is preferably 10.0%, more preferably 8.0%, Most preferably, the upper limit is 5.0%. In particular, from the viewpoint of obtaining a glass having a low glass transition point (Tg), the content of Y ₂ O ₃ may be 1.3% or less. Each component of Y ₂ O _{3, Yb} 2 _{O 3} and _Lu 2 _{O 3} is to be contained in the glass by using, for example, _Y 2 _O 3 as a raw _{material, YF 3, Yb 2 O 3} , Lu 2 O 3 , etc. it can.

In the optical glass of the present invention, the molar sum of the Ln ₂ O ₃ component (wherein Ln is one or more selected from the group consisting of La, Gd, Y, Yb, and Lu) is 10.0% or more and 40.0. % Or less is preferable. In particular, by making the molar sum of the Ln ₂ O ₃ component 10.0% or more, both the refractive index and the Abbe number of the glass can be increased, so that it is easy to obtain a glass having a desired refractive index and Abbe number. Can do. Accordingly, the lower limit of the molar sum of the Ln ₂ O ₃ component with respect to the total amount of glass in the oxide conversion composition is preferably 10.0%, more preferably 12.0%, and most preferably 15.0%. On the other hand, by making the molar sum of Ln ₂ O ₃ component below 40.0%, because the liquidus temperature of the glass is lowered, thereby reducing the devitrification of the glass. Therefore, the molar sum of the Ln ₂ O ₃ component with respect to the total amount of glass in the oxide conversion composition is preferably 40.0%, more preferably 35.0%, even more preferably 30.0%, and most preferably 27. The upper limit is 0%.

The optical glass of the present invention preferably contains two or more of the above-mentioned Ln ₂ O ₃ components. Thereby, since the liquidus temperature of glass becomes lower, glass with higher devitrification resistance can be formed. In particular, as the _Ln 2 _{O 3} component, which contains two or more components including _La 2 _{O 3} component and _Gd 2 _{O 3} component is preferable in that it can easily lower the liquidus temperature of the glass.

The Ta ₂ O ₅ component is a component that increases the refractive index of the glass and increases the devitrification resistance of the glass, and is an optional component in the optical glass of the present invention. In particular, by setting the content of the Ta ₂ O ₅ component to 20.0% or less, devitrification due to excessive inclusion of the Ta ₂ O ₅ component can be reduced. Moreover, by reducing the content of Ta ₂ O ₅ component is reduced content of expensive Ta ₂ O ₅ component, and since the raw material makes it possible to lower the temperature at which melting of the raw material and the production of optical glass Can reduce the cost. Therefore, the content of the Ta ₂ O ₅ component is preferably 20.0%, more preferably 10.0%, and most preferably 8.0% with respect to the total amount of glass in the oxide equivalent composition. In particular, in the first optical glass, the content of the Ta ₂ O ₅ component may be 4.5% or less. Although it is possible to obtain a glass having desired characteristics without containing a Ta ₂ O ₅ component, particularly in the second optical glass, the refractive index of the glass can be obtained by containing the Ta ₂ O ₅ component. While improving the devitrification resistance, the liquidus temperature of the glass can be lowered. Therefore, the content of the Ta ₂ O ₅ component in the second optical glass is preferably more than 0%, more preferably 1.0%, most preferably 2. 0% is the lower limit. The Ta ₂ O ₅ component can be contained in the glass using, for example, Ta ₂ O ₅ as a raw material.

In the second optical glass of the present invention, the content ratio of the Ta ₂ O ₅ component to the content of the WO ₃ component is preferably 1.0 or more. In particular, by setting this ratio to 1.0 or more, it is possible to suppress an increase in dispersion of the glass while maintaining the visible light transparency of the glass and increasing the refractive index. Moreover, the devitrification resistance of glass can be improved because the liquidus temperature of glass becomes low. Therefore, the molar ratio Ta ₂ O ₅ / WO ₃ of the oxide equivalent composition in the second optical glass is preferably 1.0, more preferably 2.0, still more preferably 2.1, and most preferably 2. 5 is the lower limit. On the other hand, the upper limit of this ratio is not particularly limited, and may be infinite (that is, containing no WO ₃ component). However, by setting this ratio to 10.0 or less, the content of expensive Ta ₂ O ₅ components is reduced, so that the cost for raw materials and production of optical glass can be reduced. Therefore, the molar ratio Ta ₂ O ₅ / WO ₃ of the oxide equivalent composition in the second optical glass is preferably 10.0, more preferably 7.0, and most preferably 4.0.

The SiO ₂ component is a component that increases the viscosity of the molten glass and reduces devitrification (generation of crystals) which is undesirable as an optical glass by promoting stable glass formation, and is an optional component in the optical glass of the present invention. It is an ingredient. In particular, when the content of the SiO ₂ component is 25.0% or less, an increase in the glass transition point (Tg) can be suppressed, and the high refractive index targeted by the present invention can be easily obtained. Accordingly, the content of the SiO ₂ component with respect to the total amount of glass in the oxide conversion composition is preferably 25.0%, more preferably 19.0%, still more preferably 17.5%, and most preferably 13.0%. Is the upper limit. Note that even without containing a SiO ₂ component it is possible to obtain a glass having the desired properties, particularly in the second optical glass, by containing a SiO ₂ component, the liquidus temperature of the glass is lowered Therefore, devitrification of the glass can be reduced. Moreover, glass can be easily formed by increasing the viscosity of the molten glass. Accordingly, the content of the SiO ₂ component with respect to the total amount of glass in the oxide conversion composition is preferably more than 0%, more preferably more than 1.0%, and most preferably more than 4.0%. SiO ₂ component may be contained in the glass by using as a raw material such as _{SiO 2, K 2 SiF 6,} Na 2 SiF 6 or the like.

The Na ₂ O component and the K ₂ O component are components that improve the meltability of the glass, lower the glass transition point, and increase the devitrification resistance of the glass, and are optional components in the optical glass of the present invention. . In particular, by making the content of the Na ₂ O component 15.0% or less and / or making the content of the K ₂ O component 10.0% or less, it is difficult to lower the refractive index of the glass, and It is possible to increase the stability of the glass and reduce the occurrence of devitrification and the like. Therefore, the upper limit of the content of the Na ₂ O component with respect to the total amount of glass in the oxide conversion composition is preferably 15.0%, more preferably 10.0%, and most preferably 5.0%. Further, the content of the K ₂ O component with respect to the total amount of glass in the oxide conversion composition is preferably 10.0%, more preferably 8.0%, and most preferably 5.0%. The Na ₂ O component and the K ₂ O component use, for example, Na ₂ CO ₃ , NaNO ₃ , NaF, Na ₂ SiF ₆ , K ₂ CO ₃ , KNO ₃ , KF, KHF ₂ , K ₂ SiF ₆ as raw materials. It can be contained in glass.

The Rn ₂ O component (wherein Rn is one or more selected from the group consisting of Li, Na, and K) is a component that improves the meltability of the glass and reduces the devitrification of the glass. Here, by making the content of the Rn ₂ O component 20.0% or less, it is difficult to lower the refractive index of the glass, and it is possible to increase the stability of the glass and reduce the occurrence of devitrification and the like. . Therefore, the upper limit of the molar sum of the Rn ₂ O component with respect to the total amount of glass in the oxide conversion composition is preferably 20.0%, more preferably 15.0%, and most preferably 10.0%.

The MgO component, CaO component, SrO component, and BaO component are components that adjust the refractive index, meltability, and devitrification of the glass, and are optional components in the optical glass of the present invention. In particular, by making the content of each of the MgO component, CaO component, SrO component and BaO component 10.0% or less, it becomes easy to obtain a desired refractive index, and loss of glass due to excessive inclusion of these components. The occurrence of see-through can be reduced. Therefore, the content of each of the MgO component, the CaO component, the SrO component, and the BaO component with respect to the total glass material amount of the oxide conversion composition is preferably 10.0%, more preferably 8.0%, and most preferably 5. The upper limit is 0%. The MgO component is contained in the glass using, for example, MgCO ₃ , MgF ₂ , CaCO ₃ , CaF ₂ , Sr (NO ₃ ) ₂ , SrF ₂ , BaCO ₃ , Ba (NO ₃ ) ₂ , BaF _{2 and the} like as raw materials. be able to.

  In the optical glass of the present invention, the total content of RO components (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, and Ba) is preferably 11.0% or less. Thereby, a desired refractive index can be easily obtained. Therefore, the molar sum of the RO component with respect to the total amount of glass in the oxide conversion composition is preferably 11.0%, more preferably 8.0%, and still more preferably 5.0%.

The GeO ₂ component is a component having an effect of increasing the refractive index of the glass and improving the devitrification resistance, and is an optional component in the optical glass of the present invention. However, since the raw material price of GeO ₂ is high, the production cost increases when the amount of GeO ₂ is large, thereby reducing the effect of reducing the Ta ₂ O ₅ component. Therefore, the content of the GeO ₂ component with respect to the total glass material amount of the oxide conversion composition is preferably 10.0%, more preferably 5.0%, and most preferably 1.0%. The GeO ₂ component can be contained in the glass using, for example, GeO ₂ as a raw material.

P ₂ O ₅ component is a component having an effect of improving resistance to devitrification and lower the liquidus temperature of the glass, an optional component of the optical glass of the present invention. In particular, by setting the content of the P ₂ O ₅ component to 10.0% or less, it is possible to suppress a decrease in chemical durability, particularly water resistance, of the glass. Therefore, the content of the P ₂ O ₅ component with respect to the total amount of glass in the oxide conversion composition is preferably 10.0%, more preferably 8.0%, and most preferably 5.0%. The P ₂ O ₅ component can be contained in the glass using, for example, Al (PO ₃ ) ₃ , Ca (PO ₃ ) ₂ , Ba (PO ₃ ) ₂ , BPO ₄ , H ₃ PO ₄ or the like as a raw material. .

The ZrO ₂ component is a component that contributes to the high refractive index and low dispersion of the glass and improves the devitrification resistance, and is an optional component in the optical glass of the present invention. However, if the amount of ZrO ₂ is too large, the devitrification resistance is deteriorated. Therefore, the content of the ZrO ₂ component is preferably 15.0%, more preferably 12.0%, and still more preferably 10.0% with respect to the total amount of glass in the oxide equivalent composition. Although it is possible to obtain a glass having desired characteristics without containing a ZrO ₂ component, the inclusion of the ZrO ₂ component makes it easy to obtain the performance of high refractive index and low dispersion, and resistance to loss. The effect of increasing permeability can be easily obtained. Therefore, particularly in the second optical glass, the content of the ZrO ₂ component is preferably more than 0%, more preferably 1.0%, most preferably 3. It is good also considering 0% as a minimum. The ZrO ₂ component can be contained in the glass using, for example, ZrO ₂ , ZrF ₄ or the like as a raw material.

The ZnO component is a component that lowers the glass transition temperature (Tg) and improves chemical durability, and is an optional component in the optical glass of the present invention. However, when a large amount of ZnO component is contained, the devitrification resistance of the glass tends to deteriorate. Therefore, the content of the ZnO component with respect to the total amount of glass having an oxide conversion composition is preferably 50.0%, more preferably 45.0%, and further preferably 40.0%. In particular, from the viewpoint of improving the stability of the glass and lowering the liquidus temperature, the content of the ZnO component with respect to the total amount of glass in the oxide conversion composition may be 27.0% or less, and less than 24.0%. Also good. Although it is possible to obtain a glass having desired characteristics without containing a ZnO component, the glass transition point is lowered by containing a ZnO component. Easy to obtain. Therefore, the content of the ZnO component with respect to the total amount of glass in the oxide conversion composition is preferably more than 0%, more preferably 5.0%, and most preferably 10.0%. The ZnO component can be contained in the glass using, for example, ZnO, ZnF ₂ or the like as a raw material.

The Bi ₂ O ₃ component is a component that increases the refractive index and decreases the glass transition point (Tg), and is an optional component in the optical glass of the present invention. In particular, by setting the content of the Bi ₂ O ₃ component to 15.0% or less, an increase in the liquidus temperature can be suppressed, so that a decrease in the devitrification resistance of the glass can be suppressed. Therefore, the content of the Bi ₂ O ₃ component with respect to the total amount of glass in the oxide conversion composition is preferably 15.0%, more preferably less than 10.0%, and most preferably less than 5.0%. And The Bi ₂ O ₃ component can be contained in the glass using, for example, Bi ₂ O ₃ as a raw material.

The TeO ₂ component is a component that increases the refractive index and decreases the glass transition point (Tg), and is an optional component in the optical glass of the present invention. However, TeO ₂ has a problem that it can be alloyed with platinum when melting a glass raw material in a crucible made of platinum or a melting tank in which a portion in contact with molten glass is formed of platinum. Accordingly, the content of the TeO ₂ component with respect to the total amount of glass in the oxide conversion composition is preferably 15.0%, more preferably less than 10.0%, and most preferably less than 5.0%. . The TeO ₂ component can be contained in the glass using, for example, TeO ₂ as a raw material.

The Al ₂ O ₃ component and the Ga ₂ O ₃ component are components that improve the chemical durability of the glass and improve the devitrification resistance of the molten glass, and are optional components in the optical glass of the present invention. In particular, by setting the content of each of _Al 2 _{O 3} component and _Ga 2 _{O 3} component to 15.0% can be weakened devitrification tendency of the glass by increasing the stability of the glass. Accordingly, the content of each of the Al ₂ O ₃ component and the Ga ₂ O ₃ component with respect to the total amount of the glass having an oxide conversion composition is preferably 15.0%, more preferably 10.0%, and most preferably 5. The upper limit is 0%. The Al ₂ O ₃ component and the Ga ₂ O ₃ component should be contained in the glass using, for example, Al ₂ O ₃ , Al (OH) ₃ , AlF ₃ , Ga ₂ O ₃ , Ga (OH) _3, etc. as raw materials. Can do.

The Sb ₂ O ₃ component is a component that defoams the molten glass and is an optional component in the optical glass of the present invention. When the amount of Sb ₂ O ₃ is too large, the transmittance in the short wavelength region of the visible light region is deteriorated. Accordingly, the Sb ₂ O ₃ component content is preferably 1.0%, more preferably 0.7%, and most preferably 0.5% with respect to the total amount of glass in the oxide equivalent composition. The Sb ₂ O ₃ component can be contained in the glass using, for example, Sb ₂ O ₃ , Sb ₂ O ₅ , Na ₂ H ₂ Sb ₂ O ₇ · 5H ₂ O, or the like as a raw material.

Incidentally, components defoamed fining glass is not limited to the above Sb ₂ O ₃ component, a known refining agents in the field of glass production, it is possible to use a defoamer or a combination thereof.

The F component is a component that lowers the glass transition point (Tg) and improves the devitrification resistance while lowering the dispersion of the glass, and is an optional component in the optical glass of the present invention. However, when the content of the F component, that is, the total amount of F substituted for some or all of one or more oxides of each of the above metal elements exceeds 6.0%, Since the volatilization amount of the component increases, it becomes difficult to obtain a stable optical constant, and it becomes difficult to obtain a homogeneous glass. Therefore, the content of the F component with respect to the total amount of glass in the oxide conversion composition is preferably 6.0%, more preferably 5.0%, and most preferably 3.0%. The F component can be contained in the glass by using, for example, ZrF ₄ , AlF ₃ , NaF, CaF ₂ or the like as a raw material.

<About ingredients that should not be included>
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.

  Other components can be added as necessary within the range not impairing the properties of the glass of the present invention. However, each transition metal component such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo, excluding Ti, Zr, Nb, W, La, Gd, Y, Yb, and Lu, is independent of each other. Or, even when it is 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. .

Moreover, since lead compounds such as PbO and arsenic compounds such as As ₂ O ₃ are components with high environmental loads, it is desirable that they are not substantially contained, that is, not contained at all except for inevitable mixing.

  Furthermore, each component of Th, Cd, Tl, Os, Be, and Se has tended to be refrained from being used as a harmful chemical material in recent years, and 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 that these are not substantially contained.

The glass composition of the present invention is not expressed directly in terms of mass% because the composition is expressed in terms of mol% with respect to the total amount of glass in the oxide-converted composition, but is required in the present invention. The composition represented by mass% of each component present in the glass composition satisfying the characteristics generally takes the following values in terms of oxide conversion.
B ₂ O ₃ component from 5.0 to 25.0 wt%, and _La 2 _{O 3} component from 10.0 to 55.0 wt%,
WO ₃ component 0 to 30.0 mass% and / or TiO ₂ component 0 to 10.0 mass% and / or Nb ₂ O ₅ component 0 to 35.0 mass% and / or Li ₂ O component 0 to 5.0 wt% and / or _Gd 2 _{O 3} component from 0 to 55.0% by weight and / or _Y 2 _{O 3} component 0 to 20.0% by weight and / or _Yb 2 _{O 3} component from 0 to 25.0% by weight and / or lu ₂ O ₃ component 0 to 20.0% by weight and / or _Ta 2 _{O 5} component from 0 to 30.0% by weight and / or SiO ₂ component 0 to 10.0% by weight and / or Na ₂ O component 0-8 0.0% by mass and / or K ₂ O component 0-8.0% by mass and / or MgO component 0-3.0% by mass and / or CaO component 0-5.0% by mass and / or SrO component 0-8 .0 wt% and / or BaO component 0 to 10.0% by weight and / or GeO ₂ formed 0 to 7.0% by weight and / or _P 2 _{O 5} component 0 to 10.0% by weight and / or ZrO ₂ component from 0 to 12.0% by weight and / or ZnO component from 0 to 30.0% by weight and / or Bi ₂ O ₃ component 0-40.0 mass% and / or TeO ₂ component 0-15.0 mass% and / or Al ₂ O ₃ component 0-12.0 mass% and / or Ga ₂ O ₃ component 0 20.0 wt% and / or _Sb 2 _{O 3} component 0-3.0 wt%
And the total amount as F of the fluoride which substituted a part or all of the 1 type (s) or 2 or more types of said each metal element as 0-3.0 mass%

[Production method]
The optical glass of the present invention is produced, for example, as follows. That is, the above raw materials are uniformly mixed so that each component is within a predetermined content range, the prepared mixture is put into a platinum crucible, and 1100-1500 ° C. in an electric furnace depending on the difficulty of melting the glass composition. It is produced by melting in the temperature range of 2 to 5 hours and homogenizing with stirring, then lowering to an appropriate temperature, casting into a mold, and slow cooling.

[Physical properties]
The optical glass of the present invention has a high refractive index (n _d ) and low dispersion. In particular, the refractive index (n _d ) of the optical glass of the present invention is preferably 1.75, more preferably 1.77, and most preferably 1.80, preferably 1.95, more preferably 1.95. 92, most preferably 1.91. Further, the Abbe number (ν _d ) of the optical glass of the present invention is preferably 30, more preferably 31, most preferably 32 as a lower limit, preferably 50, more preferably 45, and most preferably 40. . As a result, the degree of freedom in optical design is increased, and a large amount of light refraction can be obtained even if the device is made thinner.

Moreover, it is preferable that the optical glass of this invention has little coloring. In particular, when the optical glass of the present invention is represented by the transmittance of the glass, the wavelength (λ ₇₀ ) showing a spectral transmittance of 70% in a sample having a thickness of 10 mm is 450 nm or less, more preferably 430 nm or less, and most preferably. Is 420 nm or less. Further, the wavelength (λ ₅ ) exhibiting a spectral transmittance of 5% is 400 nm or less, more preferably 380 nm or less, and most preferably 370 nm or less. Further, the wavelength (λ ₈₀ ) exhibiting a spectral transmittance of 80% is 550 nm or less, more preferably 520 nm or less, still more preferably 500 nm or less, and most preferably 480 nm or less. Thereby, the absorption edge of the glass is positioned in the vicinity of the ultraviolet region, and the transparency of the glass in the visible region is enhanced. Therefore, this optical glass can be preferably used as a material for an optical element such as a lens.

  The optical glass of the present invention preferably has high devitrification resistance. In particular, the optical glass of the present invention preferably has a low liquidus temperature of 1200 ° C. or lower. More specifically, the upper limit of the liquidus temperature of the optical glass of the present invention is preferably 1200 ° C, more preferably 1180 ° C, and most preferably 1160 ° C. As a result, even if the molten glass flows out at a lower temperature, the crystallization of the produced glass is reduced, so that the devitrification resistance when the glass is formed from the molten state can be increased. The influence on the optical characteristics of the optical element can be reduced. Moreover, since the range of the temperature at which the preform material can be stably produced is widened, the preform material can be formed even when the melting temperature of the glass is lowered, and the energy consumed when forming the preform material can be suppressed. On the other hand, the lower limit of the liquidus temperature of the optical glass of the present invention is not particularly limited, but the liquidus temperature of the glass obtained by the present invention is approximately 500 ° C. or higher, specifically 550 ° C. or higher, more specifically 600. Often above ℃. In this specification, “liquid phase temperature” means that a 30 cc cullet-like glass sample is put into a platinum crucible in a platinum crucible having a capacity of 50 ml and completely melted at 1250 ° C., and the temperature is lowered to a predetermined temperature. Then, the glass surface and the presence or absence of crystals in the glass are observed immediately after taking out of the furnace and cooling to indicate the lowest temperature at which no crystals are observed. Here, the predetermined temperature represents a temperature set in increments of 10 ° C. from 1180 ° C. to 500 ° C.

  The optical glass of the present invention has a glass transition point (Tg) of 680 ° C. or lower. Thereby, since glass softens at a lower temperature, it can be easily press-molded at a lower temperature. In addition, it is possible to extend the life of the mold by reducing oxidation of the mold used for press molding. Therefore, the upper limit of the glass transition point (Tg) of the optical glass of the present invention is preferably 680 ° C., more preferably 650 ° C., and most preferably 630 ° C. The lower limit of the glass transition point (Tg) of the optical glass of the present invention is not particularly limited, but the glass transition point (Tg) of the glass obtained by the present invention is generally 100 ° C. or higher, specifically 150 ° C. or higher. More specifically, it is often 200 ° C. or higher.

  The optical glass of the present invention preferably has a yield point (At) of 720 ° C. or lower. Like the glass transition point (Tg), the yield point (At) is one of indices indicating the softening property of glass, and is an index indicating a temperature close to the press molding temperature. Therefore, by using a glass having a yield point (At) of 720 ° C. or lower, press molding at a lower temperature becomes possible, so that press molding can be performed more easily. Accordingly, the yield point (At) of the optical glass of the present invention is preferably 720 ° C, more preferably 700 ° C, and most preferably 680 ° C. The lower limit of the yield point (At) of the optical glass of the present invention is not particularly limited, but the yield point (At) of the glass obtained by the present invention is generally 150 ° C. or higher, specifically 200 ° C. or higher, more specifically. Specifically, it is often 250 ° C. or higher.

The optical glass of the present invention preferably has a low partial dispersion ratio (θg, F). More specifically, the partial dispersion ratio (θg, F) of the optical glass of the present invention is (−2.50 × 10 ⁻³ × ν _d +0.6571) ≦ with respect to the Abbe number (ν _d ) ≦ The relationship (θg, F) ≦ (−2.50 × 10 ⁻³ × ν _d +0.6971) is satisfied. Thereby, since an optical glass having a small partial dispersion ratio (θg, F) is obtained, chromatic aberration of an optical element formed from the optical glass can be reduced. The partial dispersion ratio (θg, F) of the optical glass of the present invention is preferably (−2.50 × 10 ⁻³ × ν _d +0.6571), more preferably (−2.50 × 10 ⁻³ × ν _d). +0.6591), and most preferably, (-2.50 × 10 ⁻³ × ν _d +0.6611) is the lower limit. On the other hand, the partial dispersion ratio (θg, F) of the optical glass of the present invention is preferably (−2.50 × 10 ⁻³ × ν _d +0.6971), more preferably (−2.50 × 10 ^−3). × ν _d +0.6921), most preferably (−2.50 × 10 ⁻³ × ν _d +0.6871) is set as the upper limit.

[Preform materials and optical elements]
A glass molded body can be produced from the produced optical glass by means of mold press molding such as reheat press molding or precision press molding. That is, a preform for mold press molding was prepared from optical glass, and after performing reheat press molding on this preform, polishing was performed to prepare a glass molded body, or polishing was performed. It is possible to produce a glass molded body by performing precision press molding on a preform, or a preform molded by a known floating molding or the like. In addition, the means for producing the glass molded body is not limited to these means.

  Thus, the optical glass of the present invention is useful for various optical elements and optical designs. Among them, it is particularly preferable to form a preform material from the optical glass of the present invention, and perform reheat press molding or precision press molding using the preform material to produce an optical element such as a lens or a prism. This makes it possible to form a preform material with a large diameter, so that the optical elements can be enlarged, but the imaging characteristics and projection can be performed with high definition and high accuracy when used in optical devices such as cameras and projectors. The characteristics can be realized.

Composition of Examples (No. 1 to No. 64) and Comparative Example (No. A) of the present invention, and the refractive index (n _d ), Abbe number (ν _d ), and partial dispersion ratio (θg) of these glasses , F), glass transition point (Tg), yield point (At), liquidus temperature, wavelength (λ ₅ , λ ₇₀ and λ ₈₀ ) showing spectral transmittance of 5%, 70% and 80%. 1 to Table 10. In addition, an Example (No.1-No.4) is an Example regarding 1st optical glass, and an Example (No.5-No.64) is an Example regarding 2nd optical glass. Also, the following examples are for illustrative purposes only, and are not limited to these examples.

  The glasses of Examples (No. 1 to No. 64) and Comparative Examples (No. A) of the present invention are all oxides, hydroxides, carbonates, nitrates, fluorides corresponding to the raw materials of the respective components. Select high-purity raw materials used for ordinary optical glass such as hydroxide, metaphosphate compound, etc., and weigh and mix evenly so that the proportions of the respective examples shown in Tables 1 to 10 are obtained. After that, it is put into a platinum crucible, melted in a temperature range of 1100 to 1500 ° C. for 2 to 5 hours in accordance with the melting difficulty of the glass composition, homogenized with stirring, cast into a mold or the like, and slowly cooled. And produced.

Here, the refractive index (n _d ), Abbe number (ν _d ), and partial dispersion ratio (θg, F) of the glasses of Examples (No. 1 to No. 64) and Comparative Examples (No. A) are as follows: Measurements were made based on Japan Optical Glass Industry Association Standard JOGIS01-2003. Then, with respect to the obtained Abbe number (ν _d ) and partial dispersion ratio (θg, F), the intercept when the slope a is 0.0025 in the relational expression (θg, F) = − a × ν _d + b b was determined. Here, the refractive index (n _d ), Abbe number (ν _d ), and partial dispersion ratio (θg, F) are measured by measuring the glass obtained at a slow cooling rate of -25 ° C./hr. Asked.

  Moreover, the glass transition point (Tg) and yield point (At) of the glass of an Example (No.1-No.64) and a comparative example (No.A) should measure using a horizontal type expansion measuring device. I asked for it. Here, the sample at the time of measuring used the thing of (phi) 4.8mm and length 50-55mm, and the temperature increase rate was 4 degrees C / min.

Moreover, the transmittance | permeability of the glass of an Example (No.1-No.64) and a comparative example (No.A) was measured according to Japan Optical Glass Industry Association standard JOGIS02. In the present invention, the presence / absence and degree of coloration of the glass were determined by measuring the transmittance of the glass. More specifically, a face parallel polished product having a thickness of 10 ± 0.1 mm was measured for a spectral transmittance of 200 to 800 nm in accordance with JISZ8722, and λ ₅ (wavelength when the transmittance was 5%), λ ₇₀ (transmittance). The wavelength at 70%) and λ ₈₀ (wavelength at 80% transmittance) were determined.

Moreover, the liquid phase temperature of the glass of an Example (No.1-No.64) and a comparative example (No.A) puts a 30cc cullet-like glass sample in a platinum crucible in a platinum crucible of 50 ml capacity. The glass surface and the crystals in the glass are immediately melted at 1250 ° C., lowered to any temperature set in increments of 10 ° C. from 1180 ° C. to 1000 ° C., held for 12 hours, taken out of the furnace and cooled. The lowest temperature at which no crystals were observed was determined.

As shown in Tables 1 to 10, all of the optical glasses of the examples of the present invention had a liquidus temperature of 1200 ° C. or lower, more specifically 1160 ° C. or lower, and were within a desired range. On the other hand, the glass of the comparative example (No. A) had a liquidus temperature higher than 1200 ° C. The reason why the liquid phase temperatures are different is that, unlike the comparative example (No. A), the optical glass of the example of the present invention is at least one of the TiO ₂ component, the WO ₃ component, and the Nb ₂ O ₅ component. The point which contains is mentioned. For this reason, it became clear that the optical glass of the Example of this invention has a liquidus temperature lower than a comparative example (No.A).

In addition, in the optical glass of the example of the present invention, each of λ ₇₀ (wavelength at 70% transmittance) was 450 nm or less, more specifically, 413 nm or less. In addition, in the optical glasses of the examples of the present invention, each of λ ₅ (wavelength at 5% transmittance) was 400 nm or less, more specifically 361 nm or less. The optical glasses of the examples of the present invention all had a λ ₈₀ (wavelength at 80% transmittance) of 550 nm or less, more specifically 530 nm or less. For this reason, it became clear that the optical glass of the Example of this invention has the high transmittance | permeability in a visible short wavelength, and is hard to color.

  The optical glasses of the examples of the present invention all had a glass transition point (Tg) of 680 ° C. or lower, more specifically 630 ° C. or lower, and were within a desired range. Further, the optical glass of Example (No. 8) of the present invention had a yield point (At) of 720 ° C. or less, more specifically 680 ° C. or less, and was within a desired range.

The optical glasses of the examples of the present invention all have a refractive index (n _d ) of 1.75 or more, more specifically 1.85 or more, and this refractive index (n _d ) is 1.95 or less. More specifically, it was 1.91 or less, and was within the desired range.

The optical glasses of the examples of the present invention all have an Abbe number (ν _d ) of 30 or more, more specifically 31 or more, and the Abbe number (ν _d ) of 50 or less, more specifically 41. And within the desired range.

Further, the optical glasses of the examples of the present invention all have a partial dispersion ratio (θg, F) of (−2.50 × 10 ⁻³ × ν _d +0.6571) or more, more specifically (−2.50). × 10 ⁻³ × ν _d +0.6672) or more. In the other hand, the partial dispersion ratio of the optical glass of the embodiment of the present ^{invention, (- 2.50 × 10 -3 ×} ν d +0.6971) or less, and more (-2.50 × ^{10 -3} × ν _d +0.6725) or less. Therefore, it was found that these partial dispersion ratios (θg, F) are within a desired range.

Therefore, the optical glass of the example of the present invention has high transmittance at a visible short wavelength and high devitrification resistance, while the refractive index (n _d ) and Abbe number (ν _d ) are within the desired ranges. And it became clear that it is easy to perform press molding by heat softening.

  Furthermore, using the optical glass of the example of the present invention, after performing reheat press molding, grinding and polishing were performed to process into the shape of a lens and a prism. Further, 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 the shape of a lens and a prism. In either case, the glass after heat softening did not cause problems such as opacification and devitrification, and could be stably processed into various lens and prism shapes.

  Although the present invention has been described in detail for the purpose of illustration, this embodiment is only for the purpose of illustration, and many modifications can be made by those skilled in the art without departing from the spirit and scope of the present invention. Will be understood.

Claims (18)

The glass the total amount of substance of the oxide composition in terms of the _B 2 _{O 3} component in mole percent from 20.0 to 46.0%
La ₂ O ₃ component from 13.639 to 25.0%
ZnO component 5.0-27.228 %
ZrO ₂ component 1.0-15.0%
Contains,
The content of Ta ₂ O ₅ component is 10.0% or less,
The content of the Li ₂ O component is 1.166% or less,
The content of Gd ₂ O ₃ component is 4.153% or less,
WO ₃ component content is 0.821 % or less ,
The content of GeO ₂ component is 1.0% or less,
Content of Ga ₂ O ₃ component is 0.010% or less <br/>,
The molar sum (TiO ₂ + WO ₃ + Nb ₂ O ₅ ) with respect to the total amount of glass in the oxide equivalent composition is 2.253 to 14.674%,
The molar sum of the Ln ₂ O ₃ component (wherein Ln is one or more selected from the group consisting of La, Gd, Y, Yb, and Lu) with respect to the total amount of glass in an oxide equivalent composition is 17.130% or more Ri der 30.0% or less,
Wherein _Ln 2 _{O 3} of the components, the optical glass you containing two or more components. TiO ₂ component 0 to 12.0 % and Nb ₂ O ₅ component 0 to 10.0 % in mol% with respect to the total amount of glass in the oxide conversion composition
The optical glass according to claim 1, further comprising: 3. The optical glass according to claim 1, wherein a molar sum (TiO ₂ + Nb ₂ O ₅ ) with respect to the total amount of glass having an oxide conversion composition is 5.0% or more and 14.674 % or less. The optical glass according to any one of claims 1 to 3, wherein the molar ratio WO ₃ / (TiO ₂ + Nb ₂ O ₅ + WO ₃ ) of the oxide equivalent composition is 0.107 or less. Mol% of the total amount of glass with oxide equivalent composition
Y ₂ O ₃ component 0 to 10.0%,
Yb ₂ O ₃ component 0 to 10.0% and Lu ₂ O ₃ component 0 to 10.0%
Any description of the optical glass of claims 1 to 4, further comprising the components of. Molar ratio _Ta 2 _O 5 / WO ₃ 1.0 to 10.0 in the optical glass according to any one of claims 1 to 5 which is in terms of oxide composition. The glass the total amount of substance of the oxide composition in terms of the mole% in either described optical glass of SiO ₂ component to 6 claims 1 content is less 19.0% of. Na ₂ O component 0 to 10.0% and K ₂ O component 0 to 10.0% in mol% with respect to the total amount of glass in the oxide conversion composition
Furthermore the optical glass according to any one of claims 1 to 7 containing the components of. _2. The molar sum of the Rn ₂ O component (wherein Rn is one or more selected from the group consisting of Li, Na, and K) with respect to the total amount of glass having an oxide equivalent composition is 20.0% or less. To 8. The optical glass according to any one of 8 to 8 . MgO component 0 to 10.0% in mol% with respect to the total amount of glass in the oxide conversion composition,
CaO component 0 to 10.0%,
SrO component 0 to 10.0% and BaO component 0 to 10.0%
Any description of the optical glass of claims 1 to 9, further comprising the components of. 2. The molar sum of RO components (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, and Ba) with respect to the total amount of glass in an oxide equivalent composition is 11.0% or less. To 10. The optical glass according to any one of 10 to 10 . Mol% of the total amount of glass with oxide equivalent composition
P ₂ O ₅ component from 0 to 10.0%,
B i ₂ O ₃ component 0 to less than 10.0%,
TeO ₂ component 0 to less than 10.0%,
Al ₂ O ₃ component 0 to 10.0% and Sb ₂ O ₃ component 0 to 1.0%
Each component of
The optical element according to any one of claims 1 to 11 , wherein the content of F as a substitute for a part or all of one or more oxides of each metal element is 0 to 6.0%. Glass. Has 1.75 to 1.95 of the refractive index _{(n d),} 30 or more and 50 or less Abbe number ([nu _d) The optical glass according to any one of claims 1 to 12 having a. The optical glass according to any one of claims 1 to 13 having a 680 ° C. or less of the glass transition point (Tg). The optical glass according to any one of claims 1 to 14 having a 1250 ° C. below the liquidus temperature. Preform formed of the optical glass according to any of claims 1 15. An optical element formed of the optical glass according to any of claims 1 15. An optical apparatus comprising the optical element according to claim 17 .