# Patent

## Title
Optical glass and preforms for precision press molding and optical elements made by using the glass

## Abstract

An object of the invention is to provide an optical glass for precision press having optical properties of a high refractive index and a low dispersion property and having a low molding temperature, a high devitrification resistance, an excellent molding property, and a small specific gravity. The optical glass of the invention contains, in terms of % by mass on the basis of oxides, respective components of B2O3: 10 to 20%, SiO2: 0.5 to 12%, La2O3: 25 to 50%, Gd2O3: 0 to 20%, Y2O3: 0 to 20%, provided that La2O3+Gd2O3+Y2O3: 35 to 60%, ZnO: 5 to 20%, Li2O: 0.2 to 3%, ZrO2: 0 to 0.5%, Ta2O5: 3 to 18% and WO3: 3 to 20%, and has optical constants of a refractive index nd of 1.84 to 1.86 and an Abbe number vd of 37 to 42 and a glass transition point (Tg) of 630° C. or lower.

## Background
CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation of PCT/JP08/066,222, filed on Sep. 9, 2008, and claims priority to Japanese Patent Application No. 2007-316425, filed on Dec. 6, 2007.


TECHNICAL FIELD
The present invention relates to an optical glass having a high refractive index and a low dispersion property, and a preform for precision press molding and an optical element using the same.
BACKGROUND ART
Recently, since highly precise and compact digital cameras, camera-equipped mobile-phones, and the like have been popularized, demands for weight saving and miniaturization of optical systems have been rapidly increased. In order to meet these demands, an optical design using a highly functional glass aspheric lens becomes the mainstream. In particular, a large-aperture aspheric lens using a glass showing a high refractive index and a low dispersion characteristic is important for the optical design.
The highly functional glass aspheric lens is produced by a molding method which forms an optical surface directly by press molding and does not require grinding and polishing steps. In the molding method, a glass molding preform is pressed under a high temperature. Therefore, the preform and the mold are exposed to a high-temperature and high-pressure environment. Accordingly, it is desired to suppress the glass transition temperature (Tg) and yield point temperature (Ts) of the preform to low values.
As a glass showing a high refractive index and a low dispersion characteristic, a glass containing B2O3 and La2O3 as main components is known. However, there have been a problem that the life of a noble metal-based protective film formed on a tungsten carbide (WC)-based mold base metal is short and the durability of the mold for molding does not last long since the molding temperature is generally high, and a problem that a molding cycle is long and thus productivity is low.
In order to solve the above problems, a glass containing, as main components, Li2O in addition to B2O3 and La2O3 is known. However, since it contains a large amount of rare metal elements such as La2O3, there is a problem that a stable glass is not obtained when it is intended to increase the refractive index.
In order to solve the above problems, a glass containing B2O3—SiO2—La2O3—Gd2O3—ZnO—Li2O—ZrO2 as main components has been proposed in Patent Document 1. However, a composition of a high-refractive-index glass having a refractive index of 1.79 or more is not specifically disclosed in Examples. It also involves a problem that the molding temperature is high.
Further, Patent Documents 2, 3, and 4 propose optical glasses for mold press molding containing B2O3—SiO2—La2O3—ZnO—Li2O—ZrO2—Ta2O5 as main components and having nd of 1.84 or more, an Abbe number vd of 35 or more, Tg of 630° C. or lower. However, the glasses excessively contain Ta2O5 and Gd2O3, so that they involve problems when trying to achieve low specific gravity, high refractive index, and cost saving.

    Patent Document 1: JP-2003-201143
    Patent Document 2: JP-2003-267748
    Patent Document 3: JP-2006-016293
    Patent Document 4: JP-2006-016295


DISCLOSURE OF THE INVENTION
An object of the invention is to provide an optical glass for precision press having optical properties of a high refractive index and a low dispersion property and having a low molding temperature, a high devitrification resistance, an excellent molding property, and a small specific gravity.
MEANS FOR SOLVING THE PROBLEMS
The optical glass according to a first embodiment of the invention contains, in terms of % by mass on the basis of oxides, respective components of B2O3: 10 to 20%, SiO2: 0.5 to 12%, La2O3: 25 to 50%, Gd2O3: 0 to 20%, Y2O3: 0 to 20%, provided that La2O3+Gd2O3+Y2O3: 35 to 60%, ZnO: 5 to 20%, Li2O: 0.2 to 3%, ZrO2: 0 to 0.5%, Ta2O5: 3 to 18% and WO3: 3 to 20%, and has optical constants of a refractive index nd of 1.84 to 1.86 and an Abbe number vd of 37 to 42, and a glass transition point (Tg) of 630° C. or lower.
The optical glass according to a second embodiment of the invention contains, in terms of % by mol on the basis of oxides, respective components of B2O3: 20 to 40%, SiO2: 1 to 30%, La2O3: 10 to 25%, ZnO: 10 to 35%, Ta2O5: 1 to 8%, Li2O: 0.5 to 15%, WO3: 1 to 15%, Gd2O3: 0 to 10%, Y2O3: 0 to 15%, and ZrO2: 0 to 0.5%, wherein the content of La2O3+Gd2O3+Y2O3 being 15 to 30%, and has a refractive index nd of 1.84 to 1.86, an Abbe number vd of 37 to 42, and a glass transition point (Tg) of 630° C. or lower.
ADVANTAGES OF THE INVENTION
The optical glass of the invention (hereinafter referred to as the present glass) has a high refractive index and has a refractive index nd with respect to the d line of 1.84 to 1.86 and an Abbe number vd of 37 to 42.
Moreover, the present glass has a specific gravity of 5.34 or less, which is small as a glass material of the optical constant region and thus can contribute to weight saving of optical systems.


BEST MODE FOR CARRYING OUT THE INVENTION
The reasons for setting the ranges of the respective components of the present glass will be described below. In the following description, the content means a content on the basis of total amount of the oxides contained in the composition.
In the present glass, B2O3 is a component which forms a glass skeleton and lowers the liquidus temperature TL, and is an essential component. In the present glass, the content of B2O3 is 10 to 20% by mass. When the content of B2O3 is less than 10% by mass, vitrification becomes difficult, which is hence not preferred. In order to obtain a glass having a good devitrification resistance, the content of B2O3 is controlled to 10% by mass or more. The content of B2O3 is more preferably 11% by mass or more and further preferably 12% by mass or more. When the content of B2O3 is 13% by mass or more, the liquidus temperature decreases and also the Abbe number can be increased, which is hence particularly preferred.
On the other hand, in the present glass, when the content of B2O3 exceeds 20% by mass, there is a concern that the refractive index nd decreases or that the chemical durability such as water resistance deteriorates. In the present glass, the content of B2O3 is 20% by mass or less. In the case where it is intended to increase the refractive index nd, the content of B2O3 is preferably 19% by mass and the content of B2O3 is more preferably 18% by mass. In this connection, the content of B2O3 in the present glass is 20 to 40% by mol in terms of % by mol.
The range of the content in terms of % by mol and the range of the content in terms of % by mass have not always mapping relation and there is a case where ranges which do not overlap each other may be present. In the invention, ranges which overlap each other are the best ranges. However, needless to say, the advantageous effects of the invention are exhibited even in the ranges which do not overlap each other (the same shall apply hereinafter).
In the present glass, ZnO is a component which stabilizes the glass and lowers the molding temperature and the melting temperature, and is an essential component. In the present glass, the content of ZnO is 5 to 20% by mass. When the content of ZnO is less than 5% by mass, there is a concern that the glass becomes unstable or that the molding temperature goes up. The content of ZnO is 5% by mass or more. The content of ZnO of 6% by mass or more is further preferred. On the other hand, in the present glass, when the content of ZnO exceeds 20% by mass, the stability of the glass becomes deteriorated and there is a concern of deterioration in chemical durability. The content of ZnO is preferably 19% by mass or less and the content of ZnO is further preferably 18% by mass or less. In this connection, the content of ZnO in the present glass is 10 to 35% by mol in terms of % by mol.
In the present glass, La2O3 is a component which increases the refractive index with respect to the d line (587.6 nm) (hereinafter referred to as refractive index nd) and the Abbe number vd and improves the chemical durability, and is an essential component. In the present glass, the content of La2O3 is 25 to 50% by mass. When the content of La2O3 is less than 25% by mass, there is a concern that the refractive index nd becomes too low. The content of La2O3 is preferably 28% by mass or more and further preferably 30% by mass or more.
On the other hand, when the content of La2O3 exceeds 50% by mass, vitrification tends to be difficult and there is a concern that the molding temperature goes up or the liquidus temperature TL goes up. The content of La2O3 is preferably 48% by mass or less and more preferably 46% by mass or less. In this connection, the content of La2O3 in the present glass is 10 to 25% by mol in terms of % by mol.
In the present glass, ZrO2 is not an essential component and the content is also limited to 0 to 0.5% by mass. The present inventors found that, in the case where the content of ZrO2 exceeds 0.5% by mass, the content of La2O3 cannot be increased if the content of Ta2O5 is small, and a stable glass cannot be obtained unless 20% by mass or more of Gd2O3 is contained. Also, the inventors found that, by controlling the content of ZrO2 to 0.5% by mass or less, it becomes possible to increase the content of La2O3 while decreasing the content of Gd2O3, which has a large formula weight among the rare metal components, and the content of Ta2O5, which is a rare and expensive raw material.
Namely, since it is important for obtaining a low-cost and low-specific-gravity optical glass for precision press having a high refractive index and low dispersion to limit the content of ZrO2 to 0.5% by mass or less, the content of ZrO2 is limited to 0 to 0.5% by mass. Furthermore, it is desirable to contain substantially no ZrO2. In this connection, the content of ZrO2 in the present glass is 0 to 0.5% by mol in terms of % by mol. As mentioned above, since it is important for obtaining a low-cost and low-specific-gravity optical glass for precision press having a high refractive index and low dispersion to limit the content of ZrO2 to 0.5% by mol or less, the content of ZrO2 is limited to 0 to 0.5% by mol.
In the present glass, Gd2O3 is a component which increases the refractive index nd and the Abbe number vd, and improves the stability of the glass by the simultaneous presence of La2O3. However, since gadolinium has a large atomic weight as compared with lanthanum having the same effect, increase in specific gravity is a problem. Thus, the introduction of a large amount thereof is disadvantageous for weight saving. Therefore, in the present glass, the content of Gd2O3 is limited to 0 to 20% by mass. In order to achieve a high refractive index and stabilize the glass, the content of Gd2O3 is preferably 1% by mass (0.5% by mol) or more and the content of Gd2O3 is more preferably 2% by mass (1% by mol) or more.
On the other hand, when the content of Ga2O3 exceeds 20% by mass (8% by mol), there is a concern that the liquidus temperature goes up and nd lowers. Therefore, the content of Gd2O3 is preferably 18% by mass (7% by mol) or less and more preferably 16% by mass (6.5% by mol) or less. In this connection, the content of Ga2O3 in the present glass is 0 to 10% by mol in terms of % by mol. As mentioned above, the content of Gd2O3 is preferably 0.5% by mol or more and further preferably 1% by mol or more. Also, the content of Gd2O3 is preferably 7% by mol or less and further preferably 6.5% by mol or less.
In the present glass, Y2O3 is a component which increases the refractive index nd and the Abbe number vd, and improves the stability of the glass as in the cases of La2O3 and Gd2O3. In the present glass, the content of Y2O3 is 0 to 20% by mass. The content of Y2O3 is preferably 1% by mass or more and the content of Y2O3 is further preferably 2% by mass or more. On the other hand, when the content of Y2O3 exceeds 20% by mass, there is a concern that the liquidus temperature goes up and nd lowers. Therefore, the content of Y2O3 is preferably 12% by mass or less and further preferably 10% by mass or less. In this connection, the content of Y2O3 in the present glass is 0 to 15% by mol in terms of % by mol.
In the present glass, the total content of La2O3, Gd2O3, and Y2O3 is preferably 35 to 60% by mass. When the total content is less than 35% by mass, there is a concern that the refractive index nd lowers or the chemical durability deteriorates. The total content is preferably 40% by mass or more, and the total amount is further preferably 41% by mass or less. The total amount is particularly preferably 43% by mass or more. On the other hand, when the total content exceeds 60% by mass, the vitrification tends to be difficult and there is a concern that the molding temperature goes up or the liquidus temperature TL goes up. The total content is preferably 58% by mass or less and the total content is further preferably 55% by mass or less. In this connection, the total content of La2O3, Gd2O3 and Y2O3 in the present glass is 15 to 30% by mol in terms of % by mol.
In the present glass, Li2O is a component which stabilizes the glass and lowers the precision press molding temperature and melting temperature, and is an essential component. In the present glass, the content of Li2O is 0.2 to 3% by mass. When the content of Li2O is less than 0.2% by mass, there is a concern that the molding temperature becomes too high. The content of Li2O is preferably 0.3% by mass or more and the content of Li2O is further preferably 0.5% by mass or more.
On the other hand, when the content of Li2O exceeds 3% by mass, devitrification is apt to occur and there is a concern that the chemical durability deteriorates or volatilization of components upon melting becomes vigorous. The content of Li2O is preferably 2.5% by mass or less, and the content of Li2O is further preferably 2% by mass or less. In this connection, the content of Li2O is 0.5 to 15% by mol in terms of % by mol.
In the present glass, Ta2O5 is a component which stabilizes the glass, improves the refractive index nd, and suppresses devitrification upon molding from a molten solution, and is an essential component. In the present glass, the content of Ta2O5 is 3 to 18% by mass. When the content of Ta2O5 is too small, there is a concern that the refractive index nd becomes too low or the liquidus temperature TL becomes too high. Therefore, the content of Ta2O5 is 3% by mass or more. The content of Ta2O5 is more preferably 5% by mass or more, and further preferably 8% by mass or more. On the other hand, when the content of Ta2O5 is too large, the molding temperature becomes high and the specific gravity becomes great. Furthermore, since Ta2O5 is a rare element and is limited as resources, its use in a large amount is not desirable. Moreover, since it is an expensive component, the use leads to increase in cost. Therefore, the content of Ta2O5 is 18% by mass or less. The content of Ta2O5 is more preferably 15% by mass or less and further preferably 13% by mass or less. In this connection, the content of Ta2O5 in the present glass is 1 to 8% by mol in terms of % by mol.
Furthermore, from the viewpoint of reducing the specific gravity, the total content of Gd2O3 and Ta2O5 is preferably 25% by mass or less, more preferably 23% by mass or less, and further preferably 20% by mass or less. In this connection, the total content of Gd2O3 and Ta2O5 is preferably 12% by mol or less.
In the present glass, WO3 is a component which is effective for stabilization of the glass, improvement of the refractive index nd, and suppression of devitrification upon high-temperature molding, and is an essential component. In the present glass, the content of WO3 is 3 to 20% by mass. When the content of WO3 is less than 3% by mass, there is a concern that the refractive index nd lowers and the liquidus temperature TL goes up. The content of WO3 is preferably 4% by mass or more, and the content of WO3 is further preferably 5% by mass or more. On the other hand, when the content of WO3 exceeds 20% by mass, the Abbe number becomes small, failing to obtain the objective low dispersion characteristic. Therefore, the content of WO3 is 18% by mass or less, and the content of WO3 is further preferably 16% by mass or less. In this connection, the content of WO3 in the present glass is 1 to 15% by mol in terms of % by mol.
In the present glass, SiO2 is a component which is effective for stabilization of the glass and suppression of devitrification upon high-temperature molding, and is an essential component. In the present glass, the content of SiO2 is 0.5 to 12% by mass. When the content of SiO2 exceeds 12% by mass, there is a concern that the molding temperature becomes too high or the refractive index nd becomes too low. The content of SiO2 is preferably 12% by mass or less and more preferably 10% by mass or less.
On the other hand, in the case where it is intended to suppress the devitrification upon high-temperature molding or it is intended to adjust the viscosity, the content of SiO2 is controlled to 0.5% by mass or more. The content of SiO2 is preferably 1% by mass or more, and the content of SiO2 is more preferably more than 2% by mass. In this connection, the content of SiO2 in the present glass is 1 to 30% by mol in terms of % by mol.
In the present glass, TiO2 is not an essential component but may be present in a content of 0 to 5% by mass for the purpose of stabilization of the glass, improvement of the refractive index, suppression of devitrification upon high-temperature molding, and the like. When the content of TiO2 exceeds 5% by mass, the Abbe number vd becomes small, so that the objective low dispersion characteristic cannot be obtained. Furthermore, since the transmittance in a near ultraviolet region decreases, there is a concern that the characteristics as an optical glass are impaired. Therefore, the content of TiO2 is more preferably 3% by mass or less. In this connection, the content of TiO2 in the present glass is 0 to 8% by mol in terms of % by mol.
In the present glass, Nb2O5 is not an essential component but may be present in a content of 0 to 5% by mass for the purpose of stabilization of the glass, improvement of the refractive index, suppression of devitrification upon high-temperature molding, and the like. When the content of Nb2O5 exceeds 5% by mass, there is a concern that the Abbe number vd becomes too small or the liquidus temperature goes up. Therefore, the content of Nb2O5 is preferably 5% by mass or less. In this connection, the content of Nb2O5 is 0 to 3% by mol in terms of % by mol.
In the present glass, Yb2O3 is not an essential component but may be present in a content of 0 to 10% by mass for the purpose of improvement of the refractive index, suppression of devitrification upon high-temperature molding, and the like. When the content of Yb2O3 exceeds 10% by mass, there is a concern that the glass becomes unstable, the molding temperature becomes too high, or the specific gravity becomes too great. Therefore, the content of Yb2O3 is preferably 5% by mass or less. It is more preferred that the glass does not contain Yb2O3. In this connection, the content of Yb2O3 if contained in the present glass is preferably 8% by mol or less.
In the present glass, each of Al2O3, Ga2O3 and GeO2 is not an essential component but each may be present in a content of 0 to 10% by mass for the purpose of stabilization of the glass, adjustment of the refractive index, or the like. When the contents of Al2O3, Ga2O3 and GeO2 exceed 10% by mass, there is a concern that the Abbe number vd becomes too low. The contents of Al2O3, Ga2O3 and GeO2 are more preferably 8% by mass or less and further preferably 6% by mass or less. Further, since Ga2O3 and GeO2 are very rare and expensive components, they are desirably not present. In this connection, the content of each of Al2O3, Ga2O3 and GeO2 in the present glass is 0 to 8% by mol in terms of % by mol.
In the present glass, each of BaO, SrO, CaO and MgO is not an essential component but each may be present in a content of 0 to 15% by mass for the purpose of stabilization of the glass, increase in the Abbe number vd, lowering of the molding temperature, decrease in the specific gravity, or the like. When the content of each of BaO, SrO, CaO and MgO exceeds 15% by mass, there is a concern that the glass becomes unstable or the refractive index nd lowers. In this connection, in the case where the present glass contains BaO, SrO, CaO and/or MgO, the respective content is preferably 30% by mol or less.
The present glass substantially consists of the above components but may contain the other components within the range that does not impair the objects of the present invention. In the case where the glass contains such components, the total content of the components is preferably 10% by mass (10% by mol) or less, more preferably 8% by mass (10% by mol) or less, and further preferably 6% by mass (6% by mol) or 5% by mass (5% by mol) or less. In this connection, the total content of the other components is, as mentioned above, preferably 10% by mol or less, more preferably 8% by mol or less, and further preferably 6% by mol or 5% by mol or less in terms of % by mol.
For example, for the purpose of refining or the like, the present glass may contain Sb2O3 in a content of 0 to 1% by mass (0 to 1% by mol). In this connection, the content of Sb2O3 is 0 to 1% by mol in terms of % by mol.
Moreover, for the purpose of further stabilization of the glass, adjustment of the refractive index nd, adjustment of the specific gravity, lowering of the melting temperature, and the like, the glass may contain each component of Na2O, K2O, Rb2O or Cs2O in a total content of 0 to 5% by mass. When the total content of each component of Na2O, K2O, Rb2O or Cs2O exceeds 5% by mass, there is a concern that the glass becomes unstable, the refractive index nd lowers, the hardness decreases, or the chemical durability deteriorates. In this connection, in the case of putting importance on the hardness and the chemical durability, it is preferred that the glass does not substantially contain any component of Na2O, K2O, Rb2O or Cs2O. Here, the term “does not substantially contain” means that the components are not positively added, and this does not preclude components included as impurities in the other components (the same shall apply hereinafter). In this connection, the total content of each component of Na2O, K2O, Rb2O or Cs2O is 0 to 5% by mol in terms of % by mol.
In the present glass, optional components other than the above components can be selected depending on respective required properties. For example, in the case of putting importance on a high refractive index nd and a low glass transition point Tg, the glass may contain SnO in a content of 0 to 4% by mass (0 to 4% by mol). Similarly, in the case of putting importance on a high refractive index, the glass may contain TeO2 and/or Bi2O3 solely or in combination in an amount of 0 to 6% by mass. When the content of TeO2 and/or Bi2O3 exceeds 6% by mass, there is a concern that the glass becomes unstable or the transmittance remarkably decreases. However, in the case where it is intended to increase the Abbe number vd, it is preferred that the glass does not substantially contain any of TeO2 or Bi2O3. In this connection, the single or total content of TeO2 and/or Bi2O3 in the present glass is 0 to 10% by mol in terms of % by mol.
In the present glass, in order to reduce the environmental load, it is preferred that the glass does not substantially contain any of lead (PbO), arsine (As2O3), thallium (Tl2O), thorium (ThO2), and cadmium (CdO). Further, when the glass contains fluorine, the composition of the optical glass tends to be heterogeneous at the time of melting the glass, since it increases thermal expansion coefficient, adversely affecting mold-releasing property and molding property, and also since the component is easily volatilized. In addition, there is a problem that the durability of the mold such as a releasing film is deteriorated upon precision molding. Therefore, it is preferred that the present glass does not substantially contain fluorine either.
In the present glass, for the reasons of prevention of coloring and the like, it is preferred that the glass does not substantially contain transition metal compounds including Fe2O3 as a representative (exclusive of TiO2). Even in the case where such compounds are inevitably incorporated by way of raw materials, it is preferred that the total content of the transition metal compounds in the present glass is limited to 0.01% by mass or less.
As optical characteristics of the present glass, the refractive index nd is preferably 1.84 to 1.86. When the refractive index nd is 1.84 or more, the glass is suitable for miniaturization and decrease in thickness of lenses, which is hence preferred. The refractive index nd is more preferably 1.845 or more. On the other hand, when the refractive index nd exceeds 1.86, the Abbe number becomes too small and also the other thermal physical properties are adversely affected, which is hence not preferred. The refractive index nd is more preferably 1.855 or less. The Abbe number vd of the present glass is preferably 37 to 42. When the Abbe number vd is more than 37, the glass has a low dispersion characteristic, which is hence preferred. Moreover, when the Abbe number vd is 42 or less, the glass has a good devitrification resistance, which is hence preferred.
The glass transition temperature Tg of the present glass is 630° C. or lower. When the glass transition temperature Tg is 630° C. or lower, the deterioration of the mold upon precision press molding hardly occurs, which is hence preferred. The glass transition temperature Tg is more preferably 625° C. or lower, more preferably 620° C. or lower, and particularly preferably 600° C. or lower.
The specific gravity of the present glass is preferably 5.34 or less. When it exceeds 5.34, in the case where the glass is used as an optical element such as an optical lens, the mass of the optical system becomes too large and thus there is a concern that the driving system of the lens bears a considerable load. Therefore, the specific gravity is desirably 5.34 or less and the specific gravity is more preferably 5.32 or less. A specific gravity of 5.24 or less is further preferred.
The liquidus temperature TL of the present glass is preferably 1200° C. or lower. When the liquidus temperature TL exceeds 1200° C., the article to be molded tends to be devitrified upon high-temperature molding and the carbon and heat-resistant alloy to be used in a receiving mold for high-temperature molding are deteriorated, which is hence not preferred. The liquidus temperature TL of the present glass is more preferably 1180° C. or lower, and further preferably 1150° C. or lower. In this connection, the liquidus temperature TL is defined as a maximum temperature at which no crystals are generated from a glass molten liquid while holding at the temperature for 1 hour.
As the process for producing a preform of the present glass, there may be mentioned, as one example, a process of allowing a molten glass to flow from a tip of a nozzle disposed on a tank to form a gob having a desired mass and receiving it on a mold with surfacing it with nitrogen gas to form a preform having an ellipsoidal, spherical or the like shape, but the process is not limited thereto. Since the present glass has such characteristics as mentioned above, an optical design can be easily performed and the glass is suitable for optical elements, particularly a glass molded aspheric lens.
EXAMPLES
Specific embodiments of the invention will be illustrated with reference to the following Examples (Examples 1 to 17), but the invention is not limited thereto.
As a method for preparing a raw material, the following raw materials were blended so as to obtain a glass having a composition shown in the tables, placed in a platinum crucible, and melted at 1250 to 1350° C. for 2 hours. On this occasion, stirring was carried out with a platinum stirrer for 0.5 hours to homogenize the molten glass. After the homogenized molten glass was drawn off to form a plate, it was maintained at a temperature of Tg+10° C. for 4 hours and then gradually cooled to room temperature at a cooling rate of −1° C./min.
As the raw materials, special grade reagents manufactured by Kanto Chemical Co., Ltd. were used for boric acid, aluminum oxide, lithium carbonate, sodium carbonate, zinc oxide, magnesium oxide, calcium carbonate, and barium carbonate. With regard to lanthanum oxide and gadolinium oxide, reagents having a purity of 99.9% manufactured by Shin-Etsu Chemical Co., Ltd. were employed. With regard to tantalum oxide, silicon dioxide, tungsten oxide, and niobium oxide, reagents having a purity of 99.9% or more manufactured by Kojundo Chemical Laboratory Co., Ltd. were used.
With regard to the glass obtained, a refractive index nd at wavelength 587.6 nm (d line), a refractive index nc at wavelength 656.3 nm (C line), a refractive index nF at wavelength 486.1 nm (F line), an Abbe number vd, a glass transition point Tg (unit: ° C.), an yield point At (unit: ° C.), a liquidus temperature TL (unit: ° C.), and a specific gravity d were measured. The measurement methods thereof are described below.
Thermal characteristics (glass transition point Tg, yield point At): A sample processed into a cylindrical shape having a diameter of 5 mm and a length of 20 mm was measured at a temperature-elevating rate of 5° C./minute by means of a thermometric apparatus (manufactured by Bruker AXS Company, trade name: TD5000SA).
Optical constants (refractive index nd, Abbe number vd): A sample processed into a rectangular shape having a side length of 20 mm and a thickness of 10 mm was measured by means of a precision refractometer (manufactured by Kalnew Optical Industries, trade name: KPR-2). The Abbe number vd was determined according to the equation: {(nd−1)/(nF−nC)}.
Liquidus temperature TL: A glass processed into a cubic shape having a side length of 10 mm was placed on a platinum dish and allowed to stand in an electric furnace set at a constant temperature for 1 hour. Then, the glass taken out of the furnace was observed under an optical microscope of 100 magnifications, and the maximum temperature where no precipitation of crystals was observed was taken as the liquidus temperature TL.
Specific gravity d: A glass cut off so as to have about 20 g was measured by the Archimedes method using water by means of a specific gravity meter SGM300P manufactured by Shimadzu Corporation.
The measurement and calculation results are shown in tables below. Tables 1 to 3 show Invention Examples in terms of % by mass. Tables 4 to 6 show Invention Examples in terms of % by mol. In the following tables, “La+Gd+Y” represents the total content of La2O3, Gd2O3 and Y2O3, and “Gd+Ta” represents the total content of Gd2O3 and Ta2O5.














TABLE 1






ex. 1
ex. 2
ex. 3
ex. 4
ex. 5
ex. 6
ex. 7






















B2O3
15.2
15.4
14.2
13.0
13.0
13.1
12.8


SiO2
4.0
4.0
3.9
5.1
5.1
5.1
5.1


Li2O
1.3
1.3
1.3
1.3
1.3
1.3
0.9


ZnO
8.1
8.1
7.9
7.7
7.8
7.8
11.8


Y2O3
5.0
5.0
6.5
6.6
6.6
6.6
6.1


La2O3
35.9
39.6
35.8
36.1
36.1
37.3
33.8


Gd2O3
8.0
4.0
8.4
8.5
8.5
8.5
7.6


ZrO2
0.0
0.0
0.0
0.0
0.0
0.0
0.0


Ta2O5
9.7
9.8
9.5
9.4
9.8
8.0
10.9


Nb2O5
0.0
0.0
0.0
0.0
0.0
0.0
0.0


WO3
12.8
12.8
12.5
12.3
11.8
12.3
11.0


Total
100.0
100.0
100.0
100.0
100.0
100.0
100.0


La + Gd + Y
48.9
48.6
50.6
51.2
51.2
52.4
47.6


Gd + Ta
17.7
13.8
17.9
17.8
18.3
16.5
18.6


nd
1.8405
1.8434
1.8490
1.8507
1.8506
1.8493
1.8516


νd
40.3
40.3
39.9
39.9
40.0
40.1
39.6


Tg
585
586
586
594
594
595
593


At
636
636
638
648
648
649
649


TL
1100
1100
1130
1130
1130
1140
1120


d
5.12
5.10
5.20
5.22
5.22
5.20
5.24






















TABLE 2






ex. 8
ex. 9
ex. 10
ex. 11
ex. 12
ex. 13





















B2O3
12.9
12.7
13.0
12.0
13.1
12.9


SiO2
5.1
5.1
5.1
6.3
5.1
5.1


Li2O
1.1
0.7
1.0
1.1
1.1
1.2


ZnO
9.8
13.9
9.8
9.7
9.8
8.8


Y2O3
6.3
5.9
6.4
3.9
2.6
6.5


La2O3
35.1
32.9
35.4
37.9
39.2
35.6


Gd2O3
8.1
7.3
8.1
7.9
7.6
8.3


ZrO2
0.0
0.0
0.0
0.0
0.0
0.0


Ta2O5
10.8
11.7
10.9
10.6
10.7
10.8


Nb2O5
0.0
0.0
1.4
0.0
0.0
0.0


WO3
10.8
9.8
8.9
10.6
10.8
10.8


Total
100.0
100.0
100.0
100.0
100.0
100.0


La + Gd + Y
49.5
46.0
50.0
49.7
49.4
50.3


Gd + Ta
18.8
19.0
19.0
18.6
18.4
19.1


nd
1.8499
1.8496
1.8508
1.8501
1.8501
1.8496


νd
40.1
39.8
40.1
40.1
40.0
40.0


Tg
593
594
595
597
590
594


At
648
650
650
654
645
641


TL
1120
1130
1150
1120
1130
1130


d
5.22
5.23
5.18
5.24
5.24
5.23




















TABLE 3






ex. 14
ex. 15
ex. 16
ex. 17



















B2O3
15.6
13.6
13.6
12.7


SiO2
4.1
4.9
4.9
5.0


Li2O
1.4
0.7
0.4
1.1


ZnO
8.2
8.5
9.7
9.7


Y2O3
7.6
1.6
2.8
2.7


La2O3
40.2
36.1
34.3
39.6


Gd2O3
0.0
13.7
13.5
8.0


ZrO2
0.0
0.0
0.0
0.0


Ta2O5
9.9
10.4
10.4
10.6


Nb2O5
0.0
0.0
0.0
0.0


WO3
13.0
10.5
10.4
10.6


Total
100.0
100.0
100.0
100.0


La + Gd + Y
47.8
51.4
50.6
50.3


Gd + Ta
9.9
24.1
23.9
18.6


nd
1.8400
1.8503
1.8517
1.8540


νd
40.2
40.2
40.2
39.9


Tg
583
609
616
590


At
634
653
662
645


TL
1110
1120
1100
1150


d
5.02
5.31
5.31
5.28























TABLE 4






ex. 1
ex. 2
ex. 3
ex. 4
ex. 5
ex. 6
ex. 7






















B2O3
33.3
33.4
31.6
28.8
28.9
28.8
27.4


SiO2
10.0
10.0
10.0
13.1
13.1
13.1
12.7


Li2O
6.8
6.7
6.7
6.6
6.6
6.6
4.4


ZnO
15.0
15.0
15.0
14.8
14.8
14.8
21.9


Y2O3
3.3
3.3
4.5
4.5
4.5
4.5
4.0


La2O3
16.7
18.3
17.0
17.1
17.2
17.6
15.6


Gd2O3
3.3
1.7
3.6
3.6
3.6
3.6
3.2


ZrO2
0.0
0.0
0.0
0.0
0.0
0.0
0.0


Ta2O5
3.3
3.3
3.3
3.3
3.4
2.8
3.7


Nb2O5
0.0
0.0
0.0
0.0
0.0
0.0
0.0


WO3
8.3
8.3
8.3
8.2
7.9
8.2
7.1


Total
100.0
100.0
100.0
100.0
100.0
100.0
100.0


La + Gd + Y
23.3
23.3
25.0
25.2
25.3
25.7
22.8


Gd + Ta
6.7
5.0
6.9
6.9
7.1
6.4
6.9






















TABLE 5






ex. 8
ex. 9
ex. 10
ex. 11
ex. 12
ex. 13





















B2O3
28.3
27.0
28.6
26.2
29.0
28.6


SiO2
12.9
12.5
13.0
16.0
12.9
13.1


Li2O
5.5
3.4
5.5
5.4
5.5
6.0


ZnO
18.4
25.3
18.6
18.1
18.4
16.6


Y2O3
4.3
3.8
4.3
2.6
1.8
4.4


La2O3
16.4
14.9
16.5
17.7
18.4
16.8


Gd2O3
3.4
3.0
3.4
3.3
3.2
3.5


ZrO2
0.0
0.0
0.0
0.0
0.0
0.0


Ta2O5
3.7
3.9
3.7
3.7
3.7
3.8


Nb2O5
0.0
0.0
0.9
0.0
0.0
0.0


WO3
7.1
6.2
5.5
7.0
7.1
7.2


Total
100.0
100.0
100.0
100.0
100.0
100.0


La + Gd + Y
24.1
21.7
24.3
23.7
23.4
24.7


Gd + Ta
7.1
6.9
7.2
7.0
6.9
7.3




















TABLE 6






ex. 14
ex. 15
ex. 16
ex. 17





















B2O3
33.4
31.0
30.7
28.3



SiO2
10.0
13.1
12.9
12.9



Li2O
6.7
3.6
2.3
5.5



ZnO
15.0
16.6
18.9
18.4



Y2O3
5.0
1.1
1.9
1.9



La2O3
18.3
17.6
16.6
18.8



Gd2O3
0.0
6.0
5.9
3.4



ZrO2
0.0
0.0
0.0
0.0



Ta2O5
3.3
3.8
3.7
3.7



Nb2O5
0.0
0.0
0.0
0.0



WO3
8.3
7.2
7.1
7.1



Total
100.0
100.0
100.0
100.0



La + Gd + Y
23.3
24.7
24.4
24.1



Gd + Ta
3.3
9.8
9.6
7.1









While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
The present application is based on Japanese Patent Application No. 2007-316425 filed on Dec. 6, 2007, and the contents are incorporated herein by reference.
INDUSTRIAL APPLICABILITY
An optical glass suitable as an optical element for use in optical systems of digital cameras and the like can be provided.

## Claims

1. An optical glass comprising, in terms of % by mass on the basis of oxides, respective components of
B2O3: 10 to 20%,
SiO2: more than 2 to 12%,
La2O3: 25 to 50%,
Gd2O3: 0 to 20%,
Y2O3: 1 to 20%,
provided that La2O3+Gd2O3+Y2O3: 35 to 60%,
ZnO: 5 to 20%,
Li2O: 0.2 to 3%,
ZrO2: 0 to 0.5%,
Ta2O5: 3 to 18% and
WO3: 3 to 20%, and
having optical constants of a refractive index nd of 1.84 to 1.86 and an Abbe number vd of 37 to 42, and a glass transition point (Tg) of 630° C. or lower.

2. The optical glass according to claim 1, wherein the total content of Gd2O3 and Ta2O5 is 25% or less in terms of % by mass on the basis of oxides.

3. The optical glass according to claim 2, having a specific gravity of 5.34 or less.

4. The optical glass according to claim 1, having a specific gravity of 5.34 or less.

5. A preform for precision press molding comprising the optical glass according to claim 1.

6. An optical element obtained by precision press molding of the optical glass according to claim 1.

7. The optical glass according to claim 1, wherein B2O3 is present in the optical glass in an amount of from 13 to 18 mass %, relative to the entire mass of the oxides.

8. The optical glass according to claim 1, wherein ZnO is present in the optical glass in an amount of from 6 to 18 mass %, relative to the entire mass of the oxides.

9. The optical glass according to claim 1, wherein La2O3 is present in the optical glass in an amount of from 30 to 46 mass %, relative to the entire mass of the oxides.

10. The optical glass according to claim 1, wherein Gd2O3 is present in the optical glass in an amount of from 2 to 16 mass %, relative to the entire mass of the oxides.

11. The optical glass according to claim 1, wherein Li2O is present in the optical glass in an amount of from 0.5 to 2 mass %, relative to the entire mass of the oxides.

12. The optical glass according to claim 1, wherein Y2O3 is present in the optical glass in an amount of from 2 to 10 mass %, relative to the entire mass of the oxides.

13. The optical glass according to claim 1, having a refractive index nd of 1.845 to 1.855 and a glass transition point (Tg) of 600° C. or lower.

14. An optical glass comprising, in terms of % by mol on the basis of oxides, respective components of:
B2O3: 20 to 40%,
SiO2: 10 to 30%,
La2O3: 10 to 25%,
ZnO: 10 to 35%,
Ta2O5: 1 to 8%,
Li2O: 0.5 to 15%,
WO3: 1 to 15%,
Gd2O3: 0 to 10%,
Y2O3: 1.1 to 15%, and
ZrO2: 0 to 0.5%,
wherein the content of La2O3+Gd2O3+Y2O3 is 15 to 30%, and having a refractive index nd of 1.84 to 1.86, an Abbe number vd of 37 to 42, and a glass transition point (Tg) of 630° C. or lower.

15. The optical glass according to claim 14, wherein B2O3 is present in the optical glass in an amount of from 26.2 to 33.4 mol %, relative to the entire moles of the oxides.

16. The optical glass according to claim 14, wherein ZnO is present in the optical glass in an amount of from 14.8 to 25.3 mol %, relative to the entire moles of the oxides.

17. The optical glass according to claim 14, wherein La2O3 is present in the optical glass in an amount of from 14.9 to 18.8 mol %, relative to the entire moles of the oxides.

18. The optical glass according to claim 14, wherein Gd2O3 is present in the optical glass in an amount of from 1 to 10 mol %, relative to the entire moles of the oxides.

19. The optical glass according to claim 14, wherein Li2O is present in the optical glass in an amount of from 2.3 to 6.8 mol %, relative to the entire moles of the oxides.

20. The optical glass according to claim 14, wherein Y2O3 is present in the optical glass in an amount of from 1.1 to 5.0 mol %, relative to the entire moles of the oxides.