CN107148403B

CN107148403B - Optical glass, optical element and optical glass material

Info

Publication number: CN107148403B
Application number: CN201580057947.9A
Authority: CN
Inventors: 松本奈绪美; 藤原康裕
Original assignee: Hoya Corp
Current assignee: Hoya Corp
Priority date: 2014-10-27
Filing date: 2015-10-27
Publication date: 2021-04-27
Anticipated expiration: 2035-10-27
Also published as: JP6669663B2; WO2016068125A1; CN107148403A; JPWO2016068125A1

Abstract

The invention aims to provide optical glass with high refractive index and excellent thermal stability, an optical element composed of the optical glass and an optical glass raw material. An optical glass which is P₂O₅、B₂O₃And Al₂O₃Wherein the optical glass comprises BaO, any 1 or more selected from MgO, CaO, ZnO and SrO, and Gd₂O₃、Y₂O₃、La₂O₃And Yb₂O₃Any 1 or more of (1), P₂O₅Relative to B₂O₃The mass ratio of the content of (B) is more than 1 to 15.0, the mass ratio alpha 1 of the content of BaO to the total content of MgO, CaO, ZnO and SrO is 3.0 or less, and P₂O₅、B₂O₃And Al₂O₃Relative to Gd₂O₃、Y₂O₃、La₂O₃And Yb₂O₃The mass ratio beta 1 of the total content is more than 4.80, the refractive index nd is 1.625-1.680, and the Abbe number vd is 58-65.

Description

Optical glass, optical element and optical glass material

Technical Field

The present invention relates to a phosphate optical glass having a refractive index (nd) of 1.625 to 1.680 and an Abbe number (vd) of 58 to 65. The present invention also relates to an optical element comprising the optical glass and an optical glass material.

Background

In recent years, with the spread of imaging apparatuses such as digital cameras and monitoring cameras, there has been an increasing demand for optical elements to be mounted on these apparatuses. In particular, phosphate optical glass having a predetermined refractive index and low dispersion is effectively used as an optical element material for these image pickup devices and the like. For example, phosphate optical glasses described in patent documents 1 and 2 are known.

In the case where a further increase in refractive index and a further decrease in dispersion are to be achieved based on such phosphate optical glass, the selection of the glass component is important.

Accordingly, optical glasses are widely used as optical elements such as optical lenses or optical glass materials for optical elements. The glass is a viscous body at a glass transition temperature Tg (hereinafter sometimes referred to simply as "glass transition temperature", "Tg" or "temperature Tg") or higher, and has a property of decreasing in viscosity with an increase in temperature, that is, a property of softening by heating to a temperature higher than Tg. By utilizing this property, as a molding method of an optical element, a press molding method is known in which a glass softened by heating is pressed and molded into a desired shape. When such press molding methods are roughly classified, there are 3 methods, namely, a direct press molding method, a reheat press molding method, and a precision press molding method (also referred to as a press molding method).

Among these molding methods, the direct press molding method and the reheat press molding method are the following methods: the molten or softened glass material is press-molded in a short time, an optical element blank having a shape similar to a target optical element is molded, and then the optical element blank is ground and polished to finish the optical element. On the other hand, the precision press molding method is a method of: the method of transferring the shape of the molding surface after precision machining to the softened glass in a non-oxidizing atmosphere to produce the target optical element does not require grinding/polishing of the molded article.

In addition, the direct press molding method is a method of pressing molten glass without producing a glass material, and the reheat press molding method and the precision press molding method are the following methods: the molten glass is once cooled to solidify it, the solidified glass material is molded, and then the glass material is reheated to soften it and press molded.

In general, in the case of a method of reheating and softening a temporarily solidified glass material, such as a reheating pressing method or a precision press molding method, when the heating temperature is too high, a defect due to crystallization may occur in a molded article after pressing. Therefore, when the heating temperature is excessively lowered while avoiding crystallization of the glass, the viscosity of the glass is high, and thus defects such as a shape defect due to a shortage of the deformation amount of the glass or a breakage of the glass due to an increase of the pressing pressure for deforming the glass may occur at the time of press molding.

These problems are more pronounced in the case of the reheat press molding method in which press molding is performed at a relatively low temperature for a long time in a non-oxidizing atmosphere under precise temperature control, and in which precise temperature control is difficult and at a relatively high temperature in an open atmosphere (for example, corresponding to a glass viscosity of 10), as compared with the precision press molding method⁴～10⁶dpas · s temperature) to perform press molding in a high temperature state for a short time.

In addition, there are many surface crystals that occur on the surface of glass and internal crystals that occur entirely from the surface to the inside of glass. For optical glass, it is preferable that both surface crystallization and internal crystallization are absent or very little.

In particular, it is important for phosphate optical glass to ensure thermal stability of the glass in the production of optical elements.

In the present invention, the thermal stability of the glass includes resistance to devitrification when the glass melt is molded and resistance to devitrification when the glass once solidified is reheated.

Documents of the prior art

Patent document

Patent document 1, patent No. 4533069

Patent document 2 Japanese laid-open patent publication No. 2004-168593

Disclosure of Invention

Problems to be solved by the invention

However, in the case of phosphate optical glass, achievement of high refractive index and low dispersion is in a trade-off relationship with ensuring thermal stability of the glass. In consideration of such a trade-off relationship, for example, when a large amount of glass components for increasing the refractive index is introduced, internal crystallization of the glass tends to occur easily, and thus the quality of the glass product is deteriorated.

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found a phosphate optical glass having a high refractive index and low dispersion properties and having excellent thermal stability. Specifically, a phosphate optical glass having a high refractive index while ensuring thermal stability to such an extent that internal crystallization of the glass does not occur at the time of reheat press molding is invented.

The purpose of the present invention is to provide a phosphate optical glass having a high refractive index nd and excellent thermal stability. Further, the present invention aims to provide an optical element comprising the optical glass and an optical glass material.

That is, the gist of the present invention is as follows.

[1]An optical glass which is P₂O₅、B₂O₃And Al₂O₃Total content of [ P ]₂O₅+B₂O₃+Al₂O₃]Is 55 mass% or less of a glass, wherein,

the optical glass comprises:

BaO、

any 1 or more selected from MgO, CaO, ZnO and SrO, and

selected from Gd₂O₃、Y₂O₃、La₂O₃And Yb₂O₃Any one of the above-mentioned 1 or more species,

P₂O₅relative to B₂O₃Mass ratio of contents of [ P ]₂O₅/B₂O₃]Is more than 1 to 15.0, and,

the mass ratio alpha 1[ BaO/(MgO + CaO + ZnO + SrO) ] of the content of BaO to the total content of MgO, CaO, ZnO and SrO is 3.0 or less,

P₂O₅、B₂O₃and Al₂O₃Relative to Gd₂O₃、Y₂O₃、La₂O₃And Yb₂O₃The mass ratio of the total content of (1) (. beta.1 [ (P)₂O₅+B₂O₃+Al₂O₃)/(Gd₂O₃+Y₂O₃+La₂O₃+Yb₂O₃)]The content of the organic acid is more than 4.80,

the refractive index nd is 1.625-1.680, and the Abbe number vd is 58-65.

[2]As described above [1]The optical glass, wherein Gd₂O₃、Y₂O₃、La₂O₃And Yb₂O₃Total content of [ Gd ]₂O₃+Y₂O₃+La₂O₃+Yb₂O₃]0.5 to 11% by mass.

[3]As described above [1]Or [2]]The optical glass, wherein P₂O₅The content of (b) is 25 to 43 mass%.

[4] The optical glass according to any one of the above [1] to [3], wherein the content of BaO is 15 to 45 mass%.

[5] The optical glass according to any one of the above [1] to [4], wherein a mass ratio of a content of ZnO to a content of BaO [ ZnO/BaO ] is 0.10 to 0.33.

[6]An optical glass which is P⁵⁺、B³⁺And Al³⁺Total content of [ P ]⁵⁺+B³⁺+Al³⁺]Oxide glass of 65 cation% or less, wherein,

the optical glass comprises:

Ba²⁺、

selected from Mg²⁺、Ca²⁺、Zn²⁺And Sr²⁺Any 1 or more of, and

selected from Gd³⁺、Y³⁺、La³⁺And Yb³⁺Any one of the above-mentioned 1 or more species,

P⁵⁺relative to B³⁺Content of cation ratio [ P ]⁵⁺/B³⁺]Is more than 1 to 10.0, and,

Ba²⁺in a content relative to Mg²⁺、Ca²⁺、Zn²⁺And Sr²⁺Cation ratio of total content of alpha 2[ Ba ]²⁺/(Mg²⁺+Ca²⁺+Zn²⁺+Sr²⁺)]The content of the organic acid is below 1.50,

P⁵⁺、B³⁺and Al³⁺Relative to Gd³⁺、Y³⁺、La³⁺And Yb³⁺The cation ratio of the total content of beta 2[ (P)⁵ ⁺+B³⁺+Al³⁺)/(Gd³⁺+Y³⁺+La³⁺+Yb³⁺)]The content of the compound is more than 14.0,

the refractive index nd is 1.625-1.680, and the Abbe number vd is 58-65.

[7]As described in [6] above]The optical glass, wherein Gd³⁺、Y³⁺、La³⁺And Yb³⁺Total content of [ Gd ]³⁺+Y³⁺+La³⁺+Yb³⁺]Is 0.1 to 5.0 cation percent.

[8]As described in [6] above]Or [7 ]]The optical glass, wherein P⁵⁺、B³⁺And Al³⁺Total content of [ P ]⁵⁺+B³⁺+Al³ ⁺]Is 49 to 65 cation percent.

[9]As described in [6] above]～[8]The optical glass according to any one of the above claims, wherein P is⁵⁺The content of (A) is 20 to 50 cation%.

[10]As described in [6] above]～[9]The optical glass according to any one of the above claims, wherein Ba²⁺The content of (A) is 5 to 30 cation%.

[11]As described in [6] above]～[10]The optical glass according to any one of the above items, wherein Zn²⁺Relative to the content of Ba²⁺Cation ratio of contents [ Zn ]²⁺/Ba²⁺]0.1 to 0.6.

[12] The optical glass according to any one of the above [6] to [11], wherein the cation ratio β 2 is 14.1 to 120.0.

[13] An optical element comprising the optical glass according to any one of [1] to [12 ].

[14] An optical glass material comprising the optical glass according to any one of the above [1] to [12 ].

Effects of the invention

According to the present invention, there can be obtained an optical glass having a high refractive index (refractive index nd of 1.625 or more) and being less likely to be crystallized even when reheated under severe conditions due to its excellent thermal stability. Further, an optical element and an optical glass material made of the optical glass can be used.

Drawings

Fig. 1 is a schematic view showing a differential scanning thermal curve of an optical glass.

Detailed Description

Hereinafter, a specific embodiment of the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail. The following embodiments are examples for illustrating the present invention, and the present invention is not meant to be limited to the following. The present invention can be modified and implemented as appropriate within the scope of the gist thereof.

(embodiment 1)

In this embodiment, as the 1 st aspect of the present invention, the optical glass of the present invention will be described based on the content ratio of each component expressed by mass%. In embodiment 1, unless otherwise specified, each content is expressed by mass%.

Optical glass

The optical glass of embodiment 1 is P₂O₅、B₂O₃And Al₂O₃Total content of [ P ]₂O₅+B₂O₃+Al₂O₃]A glass of 55 mass% or less, characterized in that the optical glass comprises BaO, MgO selected from the group consisting of,Any 1 or more of CaO, ZnO and SrO, selected from Gd₂O₃、Y₂O₃、La₂O₃And Yb₂O₃Any 1 or more of (1), P₂O₅Relative to B₂O₃Mass ratio of contents of [ P ]₂O₅/B₂O₃]More than 1 to 15.0, and a mass ratio of the content of BaO to the total content of MgO, CaO, ZnO and SrO [ BaO/(MgO + CaO + ZnO + SrO) ]1]Is 3.0 or less, P₂O₅、B₂O₃And Al₂O₃Relative to Gd₂O₃、Y₂O₃、La₂O₃And Yb₂O₃The mass ratio of the total content of (1) (. beta.1 [ (P)₂O₅+B₂O₃+Al₂O₃)/(Gd₂O₃+Y₂O₃+La₂O₃+Yb₂O₃)]4.80 or more, a refractive index nd of 1.625 to 1.680, and an Abbe number vd of 58 to 65.

In general, components constituting glass can be roughly classified into a network component forming a network structure of glass and a modifying component controlling characteristics of glass. The network components contribute primarily to the stability of the glass (e.g., structural or thermal stability, meltability of the glass). Therefore, from the viewpoint of obtaining a stable glass, it is desirable to increase the proportion of the network component in the glass.

On the other hand, the modifying component mainly contributes to the functionality of the glass (for example, optical properties such as refractive index and dispersibility, and chemical durability such as weather resistance). Therefore, it is desirable to select and adjust the kind of the modifying component and the amount of the modifying component to be added, as appropriate, in accordance with the functions and properties required for the glass. However, if the ratio of the modifying component in the glass is increased, the ratio of the network component is decreased, and therefore, there is a possibility that the stability as a glass is decreased. In addition, even if the modifying component is effective from the viewpoint of improving the properties, there is a case where a small amount of the modifying component is added to significantly lower the stability of the glass.

Thus, the balance of network components and modifying components can greatly affect the stability and functionality of the glass.

Phosphate glass has been expected to be used as an optical element such as an optical lens because of its high refractive index and low dispersion property, but it has low weather resistance and cannot be used as a glass for press molding. In order to solve such a problem, in reference example 1 described in patent document 1, BaO is added as a modifying component and the proportion of BaO in the glass is increased, thereby improving the weather resistance while securing a high refractive index (refractive index nd of 1.625 or more). In the invention described in patent document 2, by introducing BaO and ZnO in large amounts as modifying components, high refractive index can be secured and weather resistance can be improved.

However, although such an optical glass has improved weather resistance and is suitable as a glass for precision press molding, crystallization due to a large amount of introduced modifying component (for example, BaO) tends to occur, and there is a problem that the thermal stability of the glass is deteriorated. Therefore, even if the glass is once well solidified, if it is softened again under severe conditions, crystallization may occur in the glass after cooling, and such a glass is not suitable for a manufacturing method of an optical element such as a reheat press molding method.

In particular, network components (e.g. P) in optical glasses₂O₅Etc.) and the ratio of modifying components (e.g., components that improve weather resistance, components that improve refractive index, etc.) increases, the thermal stability of the glass tends to deteriorate. Therefore, crystallization of the glass occurs due to reheating in the reheat press molding, and it is difficult to obtain a high refractive index phosphate glass having excellent weather resistance and thermal stability. This problem is clearly manifested when a high refractive index nd (a refractive index nd of 1.625 or more, further 1.630 or more) is to be obtained.

Then, the present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that even when the ratio of the network component is decreased or increased in the glass (P)₂O₅、B₂O₃And Al₂O₃Total content of [ P ]₂O₅+B₂O₃+Al₂O₃]55 mass% or less), the thermal stability of the glass can be improved by compounding BaO and other divalent components in a well-balanced manner, and the present invention has been completed.

That is, one of the characteristics of the optical glass of embodiment 1 is that it contains BaO and at least one kind selected from MgO, CaO, ZnO and SrO, and the mass ratio α 1[ BaO/(MgO + CaO + ZnO + SrO) ] of the BaO content to the total content of MgO, CaO, ZnO and SrO is 3.0 or less.

By setting the mass ratio α 1 in the above range, excessive introduction of the specific modified component (BaO) relative to other modified components can be suppressed, and therefore, the occurrence of crystallization due to the specific modified component can be prevented. Therefore, the thermal stability of the glass can be ensured.

According to the optical glass of embodiment 1, it is possible to effectively prevent the occurrence of internal crystallization of the glass in reheat press molding performed in an atmospheric atmosphere where precise temperature control is difficult.

In addition, one of the characteristics of the optical glass of embodiment 1 is that Gd is contained to effectively increase the refractive index (nd) and to achieve low dispersion while maintaining thermal stability₂O₃、Y₂O₃、La₂O₃And Yb₂O₃And optionally 1 or more rare earth elements of (A), and (B) P₂O₅、B₂O₃And Al₂O₃Relative to Gd₂O₃、Y₂O₃、La₂O₃And Yb₂O₃The mass ratio of the total content of (1) (. beta.1 [ (P)₂O₅+B₂O₃+Al₂O₃)/(Gd₂O₃+Y₂O₃+La₂O₃+Yb₂O₃)]Is 4.80 or more.

By making the network component (P)₂O₅、B₂O₃And Al₂O₃) Relative to the total content of the above rare earth element (Gd)₂O₃、Y₂O₃、La₂O₃And Yb₂O₃) The ratio of the total content (mass ratio β 1) of (a) to (b) is in the above range, and the balance between the network component and the total content of the rare earth element is appropriately maintained, so that the refractive index of the glass can be increased, the abbe number can be increased, and the thermal stability of the glass can be improved.

The optical glass of embodiment 1 is particularly suitable for the case where a high-refractive-index optical element is produced by the reheat press molding method.

The optical glass in embodiment 1 is a glass composition containing 2 or more kinds of metal oxides, and is collectively referred to as an optical glass regardless of form (bulk, plate, sphere, etc.) and use (material for optical element, etc.).

< glass composition >

Next, the constituent components of the optical glass of embodiment 1 will be described in detail. The glass composition can be determined by a method such as ICP-AES (Inductively Coupled Plasma Atomic Emission Spectrometry) or the like.

In the ICP-AES analysis, quantitative analysis is first performed on an element basis, and then, conversion into an oxide expression is performed based on the quantitative analysis value. The analytical value obtained by ICP-AES may include a measurement error of about. + -. 5% of the analytical value. Therefore, the value expressed by the oxide converted from the analysis value may include an error of about ± 5%.

In embodiment 1, the content (expressed as oxide) of the constituent component being 0%, or not being contained, or not being introduced means that the constituent component is not substantially contained, and means that the content of the constituent component is not more than the impurity level.

P₂O₅A network component for forming a network structure of glass is an essential component for providing thermal stability to glass that can be produced. However, if P is contained excessively, P is not contained excessively₂O₅Then, there is a tendency that: glass transition and sag temperatures, the melting temperature of the glass increases, and the refractive index and weatherability decrease. On the other handIf P is₂O₅If the content of (b) is too small, the following tendency is present: the glass has a reduced Abbe number (vd) and thus impaired low dispersion properties, and the glass has a strong tendency to devitrify, and becomes unstable. Thus, in the optical glass of the present invention, P₂O₅The upper limit of the content of (b) is preferably 43%, and more preferably 40%, 37%, 36%, 35%, and 34% in this order. In addition, P₂O₅The lower limit of the content of (b) is preferably 25%, and more preferably 27%, 29%, 30%, 31%, 32% in this order.

B₂O₃The component is a component which is very effective for improving the meltability of glass and homogenizing the glass, and is effective for improving the devitrification resistance and weather resistance of glass, improving the refractive index, and promoting the reduction of the dispersion. However, if B is introduced excessively₂O₃There is a possibility that the glass transition temperature and sag temperature are increased, resistance to devitrification is deteriorated, and the dispersibility is deteriorated. Thus, in the optical glass of the present invention, B₂O₃The upper limit of the content of (b) is preferably 15%, and more preferably 12%, 10%, 9%, 8%, and 7% in this order. In addition, if B₂O₃If the amount of (3) is too small, the melting property and devitrification resistance of the glass are deteriorated. Thus, in the optical glass of the present invention, B₂O₃The lower limit of the content of (b) is preferably 2%, and more preferably 3%, 4%, and 4.5% in this order. In the optical glass of the present invention, B is₂O₃And P₂O₅Since the glass forms a mesh structure together, it is preferable to contain B from the viewpoint of stability of the glass₂O₃As an essential component.

Al₂O₃A network component forming a network structure of glass is used as an active component for improving the weather resistance of glass. However, if the amount of the glass transition temperature is too large, the glass transition temperature and sag temperature may be high, and the stability and melting property of the glass may be deteriorated, and the refractive index may be lowered. Thus, in the optical glass of the present invention, Al₂O₃The upper limit of the content of (b) is preferably 10%, more preferably 7%, 5%,The order of 3% is preferred. In addition, Al₂O₃The lower limit of the content of (b) is preferably 0%, and more preferably 0.1%, 0.5%, 1.0%, and 1.5% in this order.

It is to be noted that if P₂O₅、B₂O₃And Al₂O₃Total content of [ P ]₂O₅+B₂O₃+Al₂O₃]If the content exceeds 55%, there is a possibility that the refractive index decreases, the melting temperature of the glass increases, and the quality deteriorates due to volatilization of the glass. On the other hand, if the total content of these components is too small, devitrification resistance is deteriorated, vitrification is difficult, and low dispersibility may be impaired. In the optical glass of the present invention, the total content [ P ]₂O₅+B₂O₃+Al₂O₃]The upper limit of (3) is 55%, and 50%, 47%, 45%, 44%, 43%, and 42% are more preferable in this order. In addition, the total content [ P ]₂O₅+B₂O₃+Al₂O₃]The lower limit of (b) is preferably 33%, and more preferably 35%, 37%, 39%, 40% in this order.

In the optical glass of the present invention, P is added from the viewpoint of imparting both low dispersion to the glass and improvement in thermal stability₂O₅Relative to B₂O₃The content ratio of (A): mass ratio [ P₂O₅/B₂O₃]Is more than 1 to 15.0. The mass ratio [ P₂O₅/B₂O₃]The upper limit of (3) is 15.0, and further preferably 12.0, 10.0, 9.0, 8.0 and 7.5. In addition, mass ratio [ P ]₂O₅/B₂O₃]The lower limit of (b) is more than 1, and preferably 1.7, 2.0, 3.0, 3.5 and 4.0. In this manner, in the optical glass of the present invention, P which is dominant in the formation of the mesh structure of the glass is caused₂O₅And B₂O₃The ratio of (A) is balanced, thereby achieving low dispersion and excellent thermal stability.

BaO is an essential component which is very effective for increasing the refractive index of the glass and improving the weather resistance by introducing an appropriate amount. However, if the amount of the compound to be introduced is too large, the following tendency is present: the thermal stability of the glass is significantly impaired, and in addition, the glass transition temperature rises and the low dispersion property is impaired. On the other hand, if the amount of incorporation is too small, a desired refractive index cannot be obtained, and weather resistance is further deteriorated. Accordingly, in the optical glass of the present invention, BaO is an essential component, and the upper limit of the content thereof is preferably 45%, and more preferably 42%, 40%, 38%, 37%, and 36% in this order. The lower limit of the BaO content is preferably 15%, and more preferably 20%, 23%, 26%, and 28% in this order.

In addition, BaO and P are added from the viewpoint of improving the thermal stability and weather resistance of the glass₂O₅Total content of [ BaO + P ]₂O₅]The upper limit of (b) is preferably 78%, and more preferably 75%, 72%, and 70% in this order. In addition, the total content [ BaO + P ]₂O₅]The lower limit of (b) is preferably 50%, and more preferably 52%, 55%, 58%, and 60% in this order.

Further, from the viewpoint of reducing the dispersion of the glass and improving the thermal stability of the glass, the content of BaO relative to B₂O₃The content ratio of (A): mass ratio [ BaO/B ]₂O₃]The upper limit of (b) is preferably 10.0, and further preferably 9.0, 8.0, 7.5 and 7.0. In addition, the mass ratio [ BaO/B ]₂O₃]The lower limit of (b) is preferably 1.0, and further preferably 2.0, 3.0, 3.5 and 4.0 in this order.

MgO is a component introduced to make glass have both high weather resistance and low dispersibility. The incorporation of a small amount of MgO has the effect of lowering the glass transition temperature, sag temperature, or liquidus temperature. However, when a large amount of the glass is introduced, the thermal stability of the glass is remarkably deteriorated, and the liquidus temperature is rather increased. Accordingly, in the optical glass of the present invention, the upper limit of the content of MgO is preferably 8%, and more preferably 6%, 5%, and 4.5% in this order. The lower limit of the content of MgO is preferably 0%, and more preferably 0.5%, 1.0%, 1.5%, and 2.0%.

In addition, with B₂O₃、Li₂Similarly, MgO contributes to the reduction of the dispersion of glass. Accordingly, in the optical glass of the present invention, it is preferable to introduce 2% or more of MgO and B into the glass without impairing the thermal stability in the reheat press molding and obtaining a desired dispersion₂O₃And Li₂Any 1 component of O. In particular, MgO, B₂O₃And Li₂The lower limit of the content of any 1 component of O is preferably 3%, 4%, 5% in this order.

CaO is a component introduced to promote low dispersion of the glass, improve the thermal stability of the glass, and lower the liquidus temperature. However, if CaO is excessively introduced, not only the chemical durability of the glass is deteriorated, but also the thermal stability of the glass is rather lowered, and the refractive index may be lowered. Accordingly, in the optical glass of the present invention, the upper limit of the content of CaO is preferably 12%, and more preferably 10%, 9%, and 8% in this order. The lower limit of the CaO content is preferably 0%, and more preferably 2%, 3%, 4%, and 5% in this order.

From the viewpoint of achieving both low dispersibility and thermal stability of the glass and weather resistance, the upper limit of the total content [ MgO + CaO ] of MgO and CaO in the optical glass of the present invention is preferably 20%, and more preferably 17%, 15%, 12%, and 11% in this order. The lower limit of the total content [ MgO + CaO ] is preferably 3%, and more preferably 4%, 5%, 6%, and 7% in this order.

SrO is an effective component for increasing the refractive index of glass without impairing the low dispersion property of glass. Further, it is effective as a component for improving the weather resistance of glass. However, if SrO is excessively introduced, there is a tendency that: the liquidus temperature rises and the thermal stability of the glass deteriorates. Accordingly, in the optical glass of the present invention, the upper limit of the SrO content is preferably 8%, and more preferably 6% and 5% in this order. The lower limit of the SrO content is preferably 0%, and more preferably 0.1%, 1.0%, and 1.5% in this order.

ZnO is a component for increasing the refractive index of glass, improving the thermal stability of glass, and lowering the liquid phase temperature and glass transition temperature by proper introduction. However, if ZnO is excessively introduced, the low dispersion property is seriously impaired, and the chemical durability of the glass is deteriorated. Accordingly, in the optical glass of the present invention, the upper limit of the content of ZnO is preferably 15%, and more preferably 13%, 12%, 11%, 10%, and 9% in this order. If the amount of ZnO to be introduced is too small, the liquidus temperature and the glass transition temperature tend to be high. Accordingly, the lower limit of the ZnO content is preferably 0%, more preferably 1%, and further preferably 2%, 3%, and 4% in this order.

The optical glass of the present invention contains, as a divalent component, not less than 1 kind selected from MgO, CaO, ZnO and SrO in addition to BaO. In this case, from the viewpoint of improving the weather resistance of the glass and obtaining desired optical characteristics, the upper limit of the total content R1 of MgO, CaO, ZnO, SrO, and BaO [ MgO + CaO + ZnO + SrO + BaO ] is preferably 65%, and more preferably 62%, 60%, 57%, and 55% in this order. The lower limit of the total content R1 is preferably 38%, and more preferably 40%, 43%, 46%, and 48% in this order.

In the optical glass of the present invention, from the viewpoint of improving the refractive index and improving the thermal stability of the glass, the ratio of the content of BaO to the total content of MgO, CaO, ZnO and SrO is set as follows: the mass ratio alpha 1[ BaO/(MgO + CaO + ZnO + SrO) ] is 3.0 or less. The upper limit of the mass ratio α 1 is preferably 2.9, and more preferably 2.8, 2.7, 2.6, and 2.5 in this order. From the viewpoint of improving the weather resistance of the glass, the lower limit of the mass ratio α 1 is preferably 1.0, and more preferably 1.2, 1.3, 1.4, and 1.5 in this order. By satisfying such a condition, the content of BaO is not significantly excessively introduced with respect to the content of other divalent components, and therefore, precipitation of crystals due to BaO can be suppressed. Therefore, by blending BaO and other divalent components in such a well-balanced manner, even when the refractive index increasing component is increased and the component forming the mesh structure is decreased, the thermal stability of the glass can be improved.

In the optical glass of the present invention in which the mass ratio α 1 is 3.0 or less, the temperature difference (Tc-Tg) between the crystallization peak temperature Tc (hereinafter, sometimes simply referred to as "crystallization peak temperature", "Tc", or "temperature Tc") and the glass transition temperature Tg, which will be described later, is large, and Tc-Tg is 150 ℃ or more. When the mass ratio α 1 is set to be within the above range, Tc — Tg increases, and when the glass is re-softened, the glass can be softened at a temperature lower than Tc, so that the glass does not crystallize, and the thermal stability of the glass can be improved.

Further, from the viewpoint of improving the thermal stability of the glass, the ratio of the content of BaO to the total content of MgO and SrO: the upper limit of the mass ratio [ BaO/(MgO + SrO) ] is preferably 45, and further preferably 42, 40 and 38 in this order. The lower limit of the mass ratio [ BaO/(MgO + SrO) ] is preferably 1, and more preferably 2, 3, 4, and 5 in this order.

In addition, from the viewpoint of improving the thermal stability of the glass and obtaining desired optical characteristics, the ratio of the total content of SrO and BaO to the total content of MgO and CaO: the upper limit of the mass ratio [ (SrO + BaO)/(MgO + CaO) ] is preferably 8, and more preferably 7, 6, 5, and 4.5 in this order. The lower limit of the mass ratio [ (SrO + BaO)/(MgO + CaO) ] is preferably 1.0, and more preferably 2.0, 2.5, and 3.0 in this order.

Among divalent components consisting of MgO, CaO, ZnO, SrO, and BaO, BaO is effective in improving the refractive index and weather resistance of the glass, but excessive introduction significantly impairs the thermal stability of the glass. On the other hand, ZnO improves the thermal stability of the glass, but excessively introduced greatly deteriorates the low dispersion property. Then, from the viewpoint of obtaining the thermal stability and desired optical constants of the glass, the ratio of the content of ZnO to the content of BaO: the upper limit of the mass ratio [ ZnO/BaO ] is preferably 0.33, and more preferably 0.30, 0.28, and 0.27 in this order. The lower limit of the mass ratio [ ZnO/BaO ] is preferably 0.10, and more preferably 0.15, 0.18, and 0.20 in this order.

Gd₂O₃、Y₂O₃、La₂O₃And Yb₂O₃All of them are components contributing to improvement in the weather resistance of the glass and increase in the refractive index. However, if these components are excessively introduced, thermal stability and homogeneity of the glass may be deteriorated, and low dispersion may be conspicuously causedIs damaged. Thus, in the optical glass of the present invention, Gd₂O₃The upper limit of the content of (b) is preferably 10%, and more preferably 9.0%, 8.5%, and 8.0% in this order. In addition, Gd₂O₃The lower limit of the content of (b) is preferably 0%, and more preferably 0.1%, 0.5%, 1.0%, 2.0%, and 3.0% in this order. Y is₂O₃The upper limit of the content of (b) is preferably 10%, and more preferably 8%, 7%, and 6% in this order. In addition, Y₂O₃The lower limit of the content of (b) is preferably 0%, and more preferably 0.5% and 1.0%. La₂O₃The upper limit of the content of (b) is preferably 10%, and more preferably 7%, 5%, and 4% in this order. In addition, La₂O₃The lower limit of the content of (b) is preferably 0%, more preferably 0.05%. Yb of₂O₃The upper limit of the content of (b) is preferably 7%, and more preferably 5%, 2%, and 1% in this order. In addition, Yb₂O₃The lower limit of the content of (b) is preferably 0%, more preferably 0.05%. Yb is to be noted₂O₃Since the near infrared region has an absorption property, when light in the near infrared region is used, it is preferable not to introduce Yb₂O₃。

In view of effectively increasing the refractive index, Gd is preferably used₂O₃、Y₂O₃、La₂O₃And Yb₂O₃Such rare earth elements are appropriately introduced. Accordingly, the optical glass of the present invention contains Gd₂O₃、Y₂O₃、La₂O₃And Yb₂O₃Any 1 or more of (a). However, if these components are excessively introduced, the following tendency is present: the thermal stability of the glass tends to be deteriorated and the low dispersion property is significantly impaired. Thus Gd₂O₃、Y₂O₃、La₂O₃And Yb₂O₃Total content of Re1 ═ Gd₂O₃+Y₂O₃+La₂O₃+Yb₂O₃]The upper limit of (3) is preferably 11%, and more preferably 9.0%, 8.5%, and 8.0% in this order. The lower limit of the total content Re1 is preferably 0.5%, and more preferably 0.7%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%. When 2 or more kinds of rare earth elements are introduced more than the single rare earth element, the thermal stability of the glass may be improved. Therefore, the optical glass of the present invention preferably contains Gd₂O₃、Y₂O₃、La₂O₃And Yb₂O₃Any 2 or more rare earth elements.

In the optical glass of the present invention, P is added so that the mass ratio α 1 is within a predetermined range, and the thermal stability of the glass is ensured and the refractive index is effectively increased₂O₅、B₂O₃And Al₂O₃The ratio of the total content of (a) to the total content of rare earth elements Re 1: mass ratio beta 1[ (P)₂O₅+B₂O₃+Al₂O₃)/Re1]Is 4.80 or more. The lower limit of the mass ratio β 1 is 4.80, and further preferably 4.90, 4.95, 5.00, 5.05 and 5.10 in this order. In the optical glass according to the example of the present invention described later, sample 35A having the smallest total rare earth element content Re1 contained 1.12 mass% of Gd₂O₃(molecular weight: 362), the mass ratio β 1 was 37.73. In general, it is easy to substitute a certain rare earth element for another rare earth element. The mass ratio beta 1 is P₂O₅+B₂O₃+Al₂O₃The value of the relative relationship with Re1, and therefore, Y is selected₂O₃In the case of equal lighter rare earth elements as Re1, the value of β 1 becomes relatively large. For example, Gd of sample 35A₂O₃Substitution by Y of small molecular weight₂O₃(molecular weight: 225.8), the mass ratio β 1 is about 60. From this viewpoint, the upper limit of the mass ratio β 1 is preferably 65, and more preferably 60, 50, 40, 30, 20, 15, 12, 10, and 8 in this order.

In the present invention, the mass ratio α 1 and the mass ratio β 1 are closely related from the viewpoint of obtaining desired optical characteristics and improving the thermal stability of the glass. This will be explained below.

Since rare earth elements are effective for increasing the refractive index of the glass, there is a possibility that the thermal stability is impaired by excessive introduction of rare earth elements, it is preferable to increase the thermal stability of the glass and reduce the total content of rare earth elements Re1 in the optical glass of the present invention. Specifically, the total content Re1 of rare earth elements that is the denominator of the mass ratio β 1 is suppressed, and the composition is adjusted so that the mass ratio β 1 is 4.80 or more, thereby improving the thermal stability.

On the other hand, the thermal stability of the glass is improved by limiting the mass ratio β 1 to a predetermined range, but the refractive index is lowered in accordance with a decrease in the total content Re1 of the rare earth element. Therefore, in the optical glass of the present invention, the refractive index is improved by increasing the amount of BaO introduced, and effectively exhibiting the function of BaO. However, if the amount of BaO introduced is too large relative to the total content of MgO, CaO, ZnO, and SrO, thermal stability is adversely impaired, and thus the upper limit of the mass ratio α 1 is limited in the present invention (the mass ratio α 1 is 3.0 or less).

In this manner, by adjusting the glass composition so that the mass ratio α 1 and the mass ratio β 1 fall within the predetermined range, desired optical characteristics can be obtained and the thermal stability of the glass can be improved.

SiO₂Is an effective component for improving chemical durability while maintaining low dispersibility. However, if the amount of the compound to be introduced is too large, the following tendency is present: the glass transition temperature and the sag temperature increase and the refractive index decreases. Thus, in the optical glass of the present invention, SiO₂The upper limit of the content of (b) is preferably 3%, more preferably 2%, still more preferably 1%, and still more preferably 0.5%. In addition, SiO₂And P₂O₅、B₂O₃、Al₂O₃Are network components, but it may not be necessary to introduce SiO into the optical glass of the present invention₂。

Li₂O is an effective component for lowering the glass transition temperature and the sag temperature, and reducing the dispersion. In particular, P is used for the purpose of reducing the dispersion of the glass₂O₅、B₂O₃And Li₂The O coexistence is very effective. However, if Li is excessively introduced₂O deteriorates the chemical durability (weather resistance, alkali resistance, etc.) of the glass, and tends to sharply decrease the refractive index. Thus, in the optical glass of the present invention, Li₂The upper limit of the content of O is preferably 6%, and more preferably 5%, 4%, 3%, 2%, 1.8%, 1.5% in this order. In addition, Li₂The lower limit of the content of O is preferably 0%, and the smaller the content is, the more preferably 0.3%, 0.5%, 1.0%, and 1.3%. In the case of manufacturing an optical element by the reheat press molding method, substantially no Li can be introduced₂O。

Na₂O and K₂O is an arbitrary component introduced for the purpose of improving the devitrification resistance of the glass, lowering the glass transition temperature, sag temperature, and liquidus temperature, and improving the meltability of the glass. Appropriate amount of Na₂O and K₂The introduction of O improves the stability of the glass and involves a decrease in the liquidus temperature and the transition temperature, but if it is excessively introduced, the chemical durability is significantly deteriorated and the refractive index tends to be decreased. Thus, in the optical glass of the present invention, Na₂The upper limit of the content of O is preferably 5%, and more preferably 3%, 2%, and 1.5% in this order. In addition, K₂The upper limit of the content of O is preferably 3%, and more preferably 2% and 1%. It is particularly preferable that Na is not substantially introduced₂O and K₂O。

If Li₂O、Na₂O and K₂When the total content of O is too small, the glass transition temperature and the sag temperature increase, and the meltability deteriorates. Therefore, in the optical glass of the present invention, Li₂O、Na₂O and K₂Total content R of O₂1＝[Li₂O+Na₂O+K₂O]The upper limit of (b) is preferably 10%, and more preferably 7%, 5%, 3%, 2%, 1.8%, 1.5% in this order. In addition, the total content R₂The lower limit of 1 is preferably 0%, and the smaller the lower limit is more preferably 0.1%, 0.5%, 1.0%. The reheating press molding method is usedIn the case of optical elements, Li₂O、Na₂O and K₂Total content R of O₂1 is preferably 2.0% or less, more preferably 1.0% or less, more preferably 0.5% or less, still more preferably 0.3% or less, still more preferably 0.1% or less, and particularly preferably substantially not introduced.

In the optical glass of the present invention, Cs as an alkali metal oxide₂Introduction of O is not always necessary, but rather undesirable because it is disadvantageous in terms of raw material cost. In addition, Cs₂O preferably does not introduce Cs because it lowers the refractive index and significantly impairs the weather resistance₂O。

In view of both meltability and thermal stability of glass, P is₂O₅The content being relative to the total content R of alkali metal oxides₂1 ratio: mass ratio [ P₂O₅/R₂1]The upper limit of (b) is preferably 120, and more preferably in the order of 110, 100 and 90. In addition, mass ratio [ P ]₂O₅/R₂1]The lower limit of (b) is preferably 7, and more preferably 10, 15, 17 and 20 in this order.

In addition, from the viewpoint of reducing the load on the environment, the optical glass of the present invention preferably contains substantially no Pb, As, Cd, U, Th, and Tl.

The optical glass of the present invention may contain halogen, i.e., F, Cl, Br, and I, as an optional component. The content thereof may be in terms of the mass fraction of anions (e.g., [ F/(O + F))]) And (4) showing. The upper limit of the content of F is preferably 8%, and more preferably 5%, 3%, 2%, 1%, 0.5%, and 0.1% in this order. The upper limits of the contents of Cl, Br and I are preferably 5%, respectively, and more preferably 3%, 2%, 1%, 0.5% and 0.1% in this order. When the glass contains a halogen, it is preferable to suppress volatilization of the glass by using B in the glass₂O₃The upper limit of (b) is 8%, preferably 5%, 3% and 1%, and most preferably substantially not contained. However, the halogen content is not limited to 1% or less. In particular, in order to suppress volatilization of components from the glass and improve homogeneity of the glass,preferably, the halogen is substantially absent.

Further, the optical glass of the present invention may contain WO₃、TiO₂、Bi₂O₃And Nb₂O₅The easily reducible component of the composition is an arbitrary component. These easily reducible components are effective components for increasing the refractive index. However, W, Ti, Bi and Nb significantly reduce the Abbe number (vd) of the glass. Therefore, the upper limit of the content of the easily reducible component is preferably 4%, and more preferably 3%, 2%, and 1% in this order. It is particularly preferable that the above-mentioned easily reducible component is not substantially introduced.

The optical glass of the present invention as described above is preferably substantially composed of a glass selected from the group consisting of P₂O₅、B₂O₃、SiO₂、Al₂O₃、Li₂O、Na₂O、K₂O、MgO、CaO、ZnO、SrO、BaO、Gd₂O₃、Y₂O₃、La₂O₃And Yb₂O₃The composition of (a). Total content of these components [ P₂O₅+B₂O₃+SiO₂+Al₂O₃+Li₂O+Na₂O+K₂O+MgO+CaO+ZnO+SrO+BaO+Gd₂O₃+Y₂O₃+La₂O₃+Yb₂O₃]Preferably 95% or more, more preferably 98% or more, more preferably 99% or more, and still more preferably 100%.

The optical glass of the present invention is preferably composed of the above components, but other components may be introduced within a range not interfering with the effect of the present invention. In the present invention, the content of inevitable impurities is not excluded.

The phrase "substantially not contained" means that the content may be less than 0.2% by mass. Since the substantially non-contained component or additive is preferably not contained in the glass, the content thereof is preferably less than 0.1 mass%, more preferably less than 0.08 mass%, still more preferably less than 0.05 mass%, still more preferably less than 0.01 mass%, and still more preferably less than 0.005 mass%.

In addition, when the optical glass of the present invention is composed of the above components and the total amount is 100% by mass, Sb may be introduced in an additive manner within 4% by mass₂O₃、SnO₂、CeO₂And the like. Sb₂O₃The upper limit of the content of (b) is preferably 4% by mass, and more preferably 3% by mass, 2% by mass, 1% by mass, 0.5% by mass, and 0.1% by mass in this order. In addition, Sb₂O₃The lower limit of the content of (b) is preferably 0%, and more preferably 0.01%, 0.02%, and 0.04% by mass in this order. Further, SnO₂、CeO₂Since the water vapor permeability of glass may be deteriorated, it is preferably introduced in an amount of 1 mass% or less, and particularly preferably not substantially introduced.

< optical characteristics (refractive index, Abbe number) > < of optical glass

The upper limit of the refractive index nd of the optical glass of the present invention is 1.680, and the order of 1.670, 1.665 and 1.660 is more preferable. The lower limit of the refractive index nd is 1.625, and the order of 1.630 and 1.635 is more preferable.

The upper limit of the abbe number vd of the optical glass of the present invention is 65, and the order of 63 and 62.5 is more preferable. The lower limit of the abbe number vd is 58, and the lower limit is preferably 59 and 60 in this order.

By using an optical element made of such a high refractive index/low dispersion optical glass to construct an optical system, the optical system can be made compact and highly functional, and chromatic aberration can be improved.

< thermal stability of optical glass >

The thermal stability of glass includes resistance to devitrification when a molten glass is molded and resistance to devitrification when a glass that has been once solidified is reheated. The resistance to devitrification in molding a glass melt is based on the liquidus temperature, and the lower the liquidus temperature, the more excellent the resistance to devitrification. In order to prevent devitrification of glass having a high liquidus temperature, it is necessary to maintain the temperature of the glass melt at a high temperature, which may cause deterioration in quality due to volatilization of glass components or reduction in productivity. Therefore, the liquidus temperature of the optical glass of the present invention is preferably 1350 ℃ or lower, more preferably 1300 ℃ or lower, further preferably 1250 ℃ or lower, further preferably 1200 ℃ or lower, and further preferably 1100 ℃ or lower.

On the other hand, regarding resistance to devitrification when the temporarily solidified glass is reheated, the higher the temperature difference (Tc-Tg) between the crystallization peak temperature Tc and the glass transition temperature Tg, the more excellent the resistance to devitrification. For example, in the reheat press molding method, it is necessary to heat the optical glass material at a temperature higher than the temperature Tg to soften the material to an appropriate viscosity (10)⁴～10⁶Around dPa · s). However, when the temperature of the glass material after heating reaches the temperature Tc, internal crystallization occurs, and therefore, a glass having a small temperature difference (Tc-Tg) is disadvantageous in that it is press-molded by reheating. On the other hand, since glass having a large temperature difference (Tc-Tg) is easily softened at a temperature lower than the temperature Tc, it can be subjected to reheat press molding without devitrification of the glass.

In general, the "Softening Point" of glass is a temperature at which glass starts to significantly deform due to its own weight, and is about 10 degrees f^7.6Temperature of viscosity of dPa · s. On the other hand, in the reheat press molding method, the "glass softening temperature Tp" (hereinafter sometimes simply referred to as "glass softening temperature", "Tp" or "temperature Tp") is a temperature higher than the "softening point", and the viscosity of the glass is 10 or more⁴～10⁶Temperature of viscosity of dPa · s. The number is 10⁴～10⁶The temperature of dPa · s can be unambiguously determined from the viscosity curve.

The glass transition temperature Tg, the crystallization peak temperature Tc, and the endothermic peak temperature Tk (hereinafter, sometimes simply referred to as "endothermic peak temperature", "Tk", or "temperature Tk") accompanying glass transition, the crystallization start temperature Tx (hereinafter, sometimes simply referred to as "crystallization start temperature", "Tx", or "temperature Tx"), which are indicators of the thermal stability of glass, will be described with reference to fig. 1.

Fig. 1 is a schematic view showing a differential scanning thermal curve of an optical glass (phosphate optical glass). In fig. 1, the horizontal axis represents temperature, and the vertical axis represents differential heat amount corresponding to heat release and absorption of glass. The glass transition temperature Tg, the endothermic peak temperature Tk accompanying glass transition, the crystallization start temperature Tx, and the crystallization peak temperature Tc are measured by a differential Scanning calorimeter [ dsc (differential Scanning calorimetry) ].

The endothermic peak temperature Tk accompanying glass transition referred to in the present invention is the temperature of the peak of the endothermic reaction occurring around Tg to (Tg +100 ℃ C.). The crystallization peak temperature Tc is a temperature at which a crystallization exothermic peak having the lowest temperature is shown when the glass is powdered and measured by differential scanning calorimetry from room temperature to a predetermined temperature at a temperature rise rate of 10 ℃/minute. The crystallization start temperature Tx is a temperature at which the crystallization peak rises toward the low temperature side.

The glass transition temperature Tg of the optical glass of the present invention is preferably in the following range. That is, the upper limit of Tg is preferably 650 ℃, and further preferably 630 ℃, 620 ℃, 610 ℃, 600 ℃, 590 ℃. The lower limit of Tg is not particularly limited, but it is preferably 420 ℃ and further preferably in the order of 440 ℃, 460 ℃, 480 ℃, 500 ℃, 530 ℃, 560 ℃.

The crystallization peak temperature Tc of the optical glass of the present invention is preferably in the following range. That is, the lower limit of Tc is preferably 650 ℃, and further preferably 670 ℃, 680 ℃, 690 ℃, 700 ℃. The upper limit of Tc is preferably 820 ℃, and further preferably 810 ℃, 800 ℃ and 790 ℃ in this order.

In general, in the press molding method, a glass raw material is heated to adjust a viscosity suitable for press molding. In particular, in the reheat press molding method, since the glass is deformed in a shorter time than in the precision press molding method, reheating is generally performed at a higher temperature to sufficiently lower the viscosity of the glass in order to enable favorable press molding.

In the short time of the press forming, if the heating temperature is insufficient and the viscosity of the glass is high, the formed product may be cracked due to the pressure during the pressing, and the deformation may be not uniformDefective shape due to the foot, and the yield may be lowered. Therefore, in order to perform favorable press molding, particularly in the reheat press molding method, it is necessary to sufficiently heat the glass material and adjust the temperature to an appropriate temperature (glass viscosity corresponding to 10:)⁴～10⁶Temperature of dPa · s).

On the other hand, when the glass is heated to a temperature higher than the crystallization peak temperature Tc of the glass, the glass molded product after press molding is crystallized (internal crystallization and surface crystallization), and may be a defective product. Therefore, when heating the glass material, it is necessary to perform heating at a temperature lower than the temperature Tc at a viscosity suitable for press molding.

However, in the case of glass which is easily crystallized by the reheating press molding method, the temperature difference between Tg and Tc is small in many cases, and if the glass is heated to a temperature at which the viscosity is suitable for press molding, the temperature may exceed Tc.

Therefore, the crystallization of the glass is more difficult to occur as the temperature difference between the temperature Tc and the temperature Tg (Tc-Tg) is larger. As shown in the examples described later, the optical glass of the present invention has a Tc-Tg of 150 ℃ or higher, and is free from internal crystallization due to reheating and excellent in thermal stability. That is, in the optical glass of the present invention, since the temperature Tc is sufficiently higher than the temperature Tg, the glass material is softened at a temperature lower than the crystallization peak temperature Tc during the reheat press molding, and crystallization does not occur.

In other words, the crystallization peak temperature Tc of the optical glass of the present invention is sufficiently higher than the glass softening temperature Tp. As shown in examples described later, no internal crystal was generated in any of the samples of the optical glass of the present invention. Therefore, when the optical glass of the present invention is used, reheat press molding under severe reheat conditions can be favorably performed.

Further, when the relationship between the temperature difference (Tc-Tg) and the temperature difference (Tc-Tp) is observed, the temperature Tp is higher than the temperature Tg, and therefore the temperature difference (Tc-Tg) is larger than the temperature difference (Tc-Tp), and it is preferable that the temperature difference is larger. The optical glass of the present invention has a glass composition as described above, and therefore, the temperature difference (Tc-Tg) is appropriately secured, the thermal stability is improved, and the temperature difference (Tc-Tg) is increased, thereby improving the productivity of reheat press molding (for example, facilitating temperature control).

In the optical glass of the present invention, the temperature difference (Tc-Tg) between the temperature Tc and the temperature Tg is preferably 150 ℃ or more, more preferably 160 ℃ or more, further preferably 180 ℃ or more, and particularly preferably 200 ℃ or more.

The temperature difference (Tc-Tp) between the temperature Tc and the temperature Tp is preferably 1 ℃ or more, and more preferably 10 ℃ or more, more preferably 20 ℃ or more, more preferably 30 ℃ or more, still more preferably 50 ℃ or more, and still more preferably 70 ℃ or more.

The optical glass of the present invention can effectively prevent the occurrence of internal crystallization by sufficiently softening the glass material at a temperature lower than the crystallization peak temperature Tc in the reheat press molding method in which the glass material is heated at a temperature higher than Tg to soften the glass material to an appropriate viscosity (10:)⁴～10⁶Around dPa · s). Further, the optical glass of the present invention is excellent in thermal stability, and therefore, is suitable for a reheat press molding method in an open atmosphere in which precise temperature control is difficult.

The thermal stability of the glass obtained by the Differential Scanning Calorimeter (DSC) can also be evaluated by the peak intensity Δ of crystallization. Specifically, the smaller the exothermic peak of crystallization, the smaller the tendency of the glass to change into crystals, and therefore the higher the thermal stability of the glass, which is preferable for the glass of the present invention. In consideration of the device sensitivity, the peak intensity Δ for crystallization can be expressed as a relative value such that the ratio of B with respect to a is B (multiple), that is, the peak intensity Δ being a ratio of B with respect to a, where a is an absolute value of the heat difference between Tk and Tg and B is an absolute value of the heat difference between Tx and Tc. Note that the height of the crystallization peak may be calculated from the difference between the heat quantity at the peak temperature and the baseline (base line) of the differential scanning calorimeter, but in this case, the peak intensity Δ of crystallization is calculated by the former method in the embodiment of the present application, because it depends on the form of drawing the baseline.

The more highly thermally stable glass that is less likely to be crystallized, the smaller the heat generation when the glass is transformed into a crystal, and therefore the smaller the peak strength Δ. Therefore, the peak intensity Δ is preferably 10 or less, more preferably 8 or less, further preferably 6 or less, further preferably 4 or less, further more preferably 2 or less, and still further more preferably 1 or less. In the most preferable glass, no crystallization peak is observed, and the peak intensity cannot be defined. Even when the peak strength Δ is small, if the temperature difference [ Tc-Tg ] between the temperature Tc and the temperature Tg is 150 ℃ or more, crystallization does not occur even when the viscosity is lowered by heating the glass to a higher temperature, and thus crystallization in reheat press molding is difficult to occur.

The optical glass of the present invention is excellent in weather resistance. The weather resistance of glass can be expressed by a haze value (haze) as an index. The haze value is a degree of clouding of the glass when the glass is held for a predetermined time in a high-temperature and high-humidity environment. Specifically, the haze value represents a ratio of a scattered light intensity to a total transmitted light intensity, i.e., "scattered light intensity/transmitted light intensity", in% when white light is allowed to vertically transmit through a polished surface of a double-sided optically polished glass plate. The optical glass of the present invention preferably has a haze value of 10 or less, more preferably a haze value of 5 or less, still more preferably a haze value of 2 or less, and still more preferably a haze value of less than 1. Glass having a high haze value is so-called glass having low chemical durability, and such glass is easily corroded by water droplets or water vapor adhering to the glass and various chemical components in the use environment, and is likely to generate a reactant on the glass surface. On the other hand, a glass having a small haze value such as the optical glass of the present invention is a glass having high chemical durability (weather resistance).

(embodiment 2)

In this embodiment, as the 2 nd aspect of the present invention, the optical glass of the present invention will be described based on the content ratio of each component expressed as cation%. In embodiment 2, each content is expressed as cation% unless otherwise specified.

In embodiment 2, the cation% represents the ratio of individual cations to all cations contained in the glass in mole percent. In addition, since the optical glass of embodiment 2 is an oxide glass, the anion is mainly oxygen (O)^2-) However, a part of the anion may be replaced with an anion other than oxygen (for example, halogen).

Optical glass

The optical glass of embodiment 2 is P⁵⁺、B³⁺And Al³⁺Total content of [ P ]⁵⁺+B³⁺+Al³⁺]An oxide glass of 65% or less, characterized by containing Ba²⁺Selected from Mg²⁺、Ca²⁺、Zn²⁺And Sr²⁺And is selected from Gd³ ⁺、Y³⁺、La³⁺And Yb³⁺Any 1 or more of (1), P⁵⁺Relative to B³⁺Content of cation ratio [ P ]⁵⁺/B³⁺]More than 1 to 10.0, Ba²⁺In a content relative to Mg²⁺、Ca²⁺、Zn²⁺And Sr²⁺Cation ratio of total content of alpha 2[ Ba ]²⁺/(Mg²⁺+Ca²⁺+Zn²⁺+Sr²⁺)]Is 1.50 or less, P⁵⁺、B³⁺And Al³⁺Relative to Gd³⁺、Y³⁺、La³⁺And Yb³⁺The cation ratio of the total content of beta 2[ (P)⁵⁺+B³⁺+Al³⁺)/(Gd³⁺+Y³⁺+La³⁺+Yb³⁺)]14.0 or more, a refractive index nd of 1.625 to 1.680, and an Abbe number vd of 58 to 65.

Phosphate glass has been expected to be used as an optical element such as an optical lens because of its high refractive index and low dispersion property, but it has low weather resistance and cannot be used as a glass for press molding. In order to solve such a problem, Ba is added in reference example 1 described in patent document 1²⁺As a modifying component and adding Ba in the glass²⁺The ratio of (a) is large, and weather resistance is improved while securing a high refractive index (refractive index nd of 1.625 or more). In addition, in the invention described in patent document 2, Ba is introduced in large amounts²⁺And Zn²⁺As a modifying component, a high refractive index can be secured and weather resistance can be improved.

However, such an optical glass has improved weather resistance and is suitable as a glass for precision press molding, but a large amount of a modifying component (for example, Ba) introduced therein is likely to be generated²⁺) The crystallization caused thereby has a problem that the thermal stability of the glass is deteriorated. Therefore, even if the glass is once well solidified, if it is softened again under severe conditions, crystallization may occur in the glass after cooling, and such a glass is not suitable for a manufacturing method of an optical element such as a reheat press molding method.

In particular, network components (e.g. P) in optical glasses⁵⁺Etc.) and modifying the component (e.g., increasingWeather resistance component, refractive index-improving component, etc.) increases, the thermal stability of the glass tends to deteriorate. Therefore, crystallization of the glass occurs due to reheating in the reheat press molding, and it is difficult to obtain a high refractive index phosphate glass having excellent weather resistance and thermal stability. This problem is clearly manifested when a high refractive index nd (a refractive index nd of 1.625 or more, further 1.630 or more) is to be obtained.

Then, the present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that even when the ratio of the network component is decreased or increased in the glass (P)⁵⁺、B³⁺And Al³⁺Total content of [ P ]⁵⁺+B³⁺+Al³⁺]65% or less) of Ba is mixed in a well-balanced manner²⁺And other divalent components, can improve the thermal stability of the glass, thereby completing the present invention.

That is, one of the features of the optical glass of the present invention is that it contains Ba²⁺At the same time, contains Mg²⁺、Ca²⁺、Zn²⁺And Sr²⁺1 or more of Ba²⁺Relative to the content of Mg²⁺、Ca²⁺、Zn²⁺And Sr²⁺The mass ratio of the total content of (B) alpha 2[ Ba²⁺/(Mg²⁺+Ca²⁺+Zn²⁺+Sr²⁺)]Is 1.50 or less.

By setting the cation ratio α 2 in the above range, a specific modified component (Ba) can be suppressed²⁺) Since the modified substance is introduced in excess of other modified substances, the occurrence of crystallization due to a specific modified substance can be prevented. Therefore, the thermal stability of the glass can be ensured.

According to the optical glass of the present invention, it is possible to effectively prevent the occurrence of internal crystallization of the glass in reheat press molding in an atmospheric atmosphere in which precise temperature control is difficult.

In addition, one of the characteristics of the optical glass of the present invention is that Gd is contained to effectively increase the refractive index (nd) and to realize low dispersion while maintaining thermal stability³⁺、Y³⁺、La³⁺And Yb³⁺And optionally 1 or more rare earth elements of (A), and (B) P⁵⁺、B³⁺And Al³⁺Relative to Gd³⁺、Y³⁺、La³⁺And Yb³⁺The cation ratio of the total content of beta 2[ (P)⁵⁺+B³⁺+Al³⁺)/(Gd³⁺+Y³⁺+La³⁺+Yb³⁺)]Is 14.0 or more.

By making the network component (P)⁵⁺、B³⁺And Al³⁺) Relative to the total content of the above rare earth element (Gd)³⁺、Y³⁺、La³⁺And Yb³⁺) The ratio of the total content (cation ratio β 2) of (a) is in the above range, and the balance between the network component and the total content of the rare earth element is appropriately maintained, so that the refractive index of the glass can be increased, the abbe number can be increased, and the thermal stability of the glass can be improved.

The optical glass of embodiment 2 is particularly suitable for the case where a high-refractive-index optical element is produced by the reheat press molding method.

The optical glass in embodiment 2 is a glass composition containing 2 or more kinds of metal oxides, and is collectively referred to as an optical glass regardless of form (bulk, plate, sphere, etc.) and use (raw material for optical element, etc.).

< glass composition >

Next, the glass composition of the optical glass of embodiment 2 will be described in detail. The content of the constituent components of the glass can be measured by a method such as ICP-AES (Inductively Coupled Plasma Atomic Emission Spectrometry) or the like.

In addition, an analytical value (for example, in atomic%) obtained by quantitative analysis of each element based on ICP-AES analysis may include a measurement error of about ± 5% of the analytical value. The conversion method is described later, and the conversion method is a method of converting the cation component in the glass into a value expressed as a cation% based on the above analyzed value.

In embodiment 2, the content of a constituent component being 0%, or not being contained, or not being introduced means that the constituent component is not substantially contained, and means that the content of the constituent component is not more than the impurity level.

P⁵⁺A network component for forming a network structure of glass is an essential component for providing thermal stability to glass that can be produced. However, if P is contained excessively, P is not contained excessively⁵⁺Then, there is a tendency that: glass transition and sag temperatures, the melting temperature of the glass increases, and the refractive index and weatherability decrease. On the other hand, if P⁵⁺If the content of (b) is too small, the following tendency is present: the glass has a reduced Abbe number (vd) and thus impaired low dispersion properties, and the glass has a strong tendency to devitrify, and becomes unstable. Thus, in the optical glass of the present invention, P⁵⁺The upper limit of the content of (b) is preferably 50%, and more preferably 45%, 42%, 40%, 39%, and 38% in this order. In addition, P⁵⁺The lower limit of the content of (b) is preferably 20%, and more preferably 25%, 27%, 30%, 32%, and 34% in this order.

B³⁺The component is a component which is very effective for improving the meltability of glass and homogenizing the glass, and is effective for improving the devitrification resistance and weather resistance of glass, improving the refractive index, and promoting the reduction of the dispersion. However, if B is introduced excessively³⁺There is a possibility that the glass transition temperature and sag temperature are increased, resistance to devitrification is deteriorated, and the dispersibility is deteriorated. Thus, in the optical glass of the present invention, B³⁺The upper limit of the content of (b) is preferably 25%, and more preferably 22%, 20%, 18%, 17%, 16% in this order. In addition, if B³⁺If the amount of (3) is too small, the melting property and devitrification resistance of the glass are deteriorated. Thus, in the optical glass of the present invention, B³⁺The lower limit of the content of (b) is preferably 1%, and more preferably 2.0%, 3.0%, 5.0%, 8.0%, and 10% in this order. In the optical glass of the present invention, B is³⁺And P⁵⁺Since the glass forms a mesh structure together, it is preferable to contain B from the viewpoint of stability of the glass³⁺As an essential component.

Al³⁺A network component forming a network structure of glass is used as an active component for improving the weather resistance of glass. However, if the amount of the glass transition temperature is too large, the glass transition temperature and sag temperature may be high, and the stability and melting property of the glass may be deteriorated, and the refractive index may be lowered. Thus, in the optical glass of the present invention, Al³⁺The upper limit of the content of (b) is preferably 13%, and more preferably 10%, 8%, 7%, and 6% in this order. In addition, Al³⁺The lower limit of the content of (b) is preferably 0%, and more preferably 0.1%, 0.5%, 1.0%, and 2.0% in this order.

It is to be noted that if P⁵⁺、B³⁺And Al³⁺Total content of [ P ]₂O₅+B₂O₃+Al₂O₃]If the content exceeds 65%, there is a possibility that the refractive index decreases, the melting temperature of the glass increases, and the quality deteriorates due to volatilization of the glass. On the other hand, if the total content of these components is too small, devitrification resistance is deteriorated, vitrification is difficult, and low dispersibility may be impaired. In the optical glass of the present invention, the total content [ P ]⁵⁺+B³⁺+Al³⁺]The upper limit of (3) is 65%, and preferably 60%, 58%, 57% and 56% in this order. Total content [ P⁵⁺+B³⁺+Al³⁺]The lower limit of (b) is preferably 40%, and more preferably 45%, 47%, 49%, and 50% in this order.

In the optical glass of the present invention, P is added from the viewpoint of imparting both low dispersion to the glass and improvement in thermal stability⁵⁺Relative to B³⁺The content ratio of (A): cation ratio [ P ]⁵⁺/B³⁺]Is more than 1 to 10.0. In addition, the cation ratio [ P ]⁵⁺/B³⁺]The preferable upper limit of (3) is 8.0, and further 6.0, 5.0, 4.5, 4.0 and 3.7 are preferable in this order. In addition, the cation ratio [ P ]⁵⁺/B³⁺]The lower limit of (3) is preferably 1.2, and more preferably 1.5 and 2.0 in this order. In this manner, in the optical glass of the present invention, P which is dominant in the formation of the mesh structure of the glass is caused⁵⁺And B³⁺The ratio of (A) is balanced, thereby achieving low dispersion and excellent thermal stability.

Ba²⁺Is an essential component which is very effective for improving the refractive index and weather resistance of the glass by introducing an appropriate amount. However, if the amount of the compound to be introduced is too large, the following tendency is present: the thermal stability of the glass is significantly impaired, and in addition, the glass transition temperature rises and the low dispersion property is impaired. On the other hand, if the amount of incorporation is too small, a desired refractive index cannot be obtained, and weather resistance is further deteriorated. Thus, in the optical glass of the present invention, Ba²⁺The upper limit of the content is preferably 30% as an essential component, and more preferably 27%, 25%, 22%, 20%, 19%, and 18% in this order. In addition, Ba²⁺The lower limit of the content of (b) is preferably 5.0%, and more preferably 8.0%, 10%, 12%, and 14% in this order.

In addition, Ba is a compound of Ba in view of improving thermal stability and weather resistance of the glass²⁺And P⁵⁺Total content of [ Ba ]²⁺+P⁵ ⁺]The upper limit of (b) is preferably 65%, and more preferably 60%, 58%, and 56% in this order. In addition, the total content [ Ba ]²⁺+P⁵⁺]The lower limit of (b) is preferably 40%, and more preferably 42%, 45%, 48%, and 50% in this order.

Further, from the viewpoint of reducing the dispersion of the glass and improving the thermal stability of the glass, B³⁺Relative to the content of Ba²⁺The content ratio of (A): cation ratio [ Ba ]²⁺/B³⁺]The upper limit of (b) is preferably 3.0, and more preferably 2.5, 2.0, 1.8 and 1.7 in this order. In addition, cation ratio [ Ba ]²⁺/B³⁺]The lower limit of (b) is preferably 0.5, and more preferably 0.6, 0.8, and 1.0 in this order.

Mg²⁺Is a component introduced for the purpose of achieving both high weatherability and low dispersibility in glass. By small amounts of Mg²⁺The introduction of (2) has an effect of lowering the glass transition temperature, the sag temperature, or the liquidus temperature. However, when a large amount of the glass is introduced, the thermal stability of the glass is remarkably deteriorated, and the liquidus temperature is rather increased. Thus, in the optical glass of the present invention, Mg²⁺The upper limit of the content of (b) is preferably 20%, and more preferably 15%, 12%, 10%, and 9% in this order. In addition, Mg²⁺The lower limit of the content of (b) is preferably 0%, and more preferably 0.5%, 1.0%, 1.5%, and 2.0% in this order.

Ca²⁺The components are introduced to promote low dispersion of the glass, improve the thermal stability of the glass, and lower the liquid phase temperature. However, if Ca is introduced excessively²⁺Not only does the chemical durability of the glass deteriorate, but the thermal stability of the glass also decreases, and the refractive index may also decrease. Thus, in the optical glass of the present invention, Ca²⁺The upper limit of the content of (b) is preferably 22%, and more preferably 18%, 15%, 12%, 11%, and 10% in this order. In addition, Ca²⁺The lower limit of the content of (b) is preferably 0%, and more preferably 1.0%, 3.0%, 5.0%, 6.0%, and 7.0% in this order.

In the optical glass of the present invention, Mg is contained in the glass from the viewpoint of achieving both of low dispersion and thermal stability of the glass and weather resistance²⁺And Ca²⁺Total content of [ Mg²⁺+Ca²⁺]The upper limit of (b) is preferably 30%, and more preferably 27%, 25%, 22%, 20%, and 18% in this order. In addition, total content [ Mg²⁺+Ca²⁺]The lower limit of (b) is preferably 2%, and more preferably 3.0%, 5.0%, 8.0%, and 10% in this order.

Sr²⁺An effective component for increasing the refractive index of the glass without impairing the low dispersion property of the glass. Further, it is effective as a component for improving the weather resistance of glass. However, if Sr is excessively introduced²⁺Then, there is a tendency that: the liquidus temperature rises and the thermal stability of the glass deteriorates. Thus, in the optical glass of the present invention, Sr²⁺The upper limit of the content of (b) is preferably 10%, and more preferably 8%, 5%, 4%, and 3% in this order. In addition, Sr²⁺The lower limit of the content of (b) is preferably 0%, and more preferably 0.5%, 1.0%, 1.5%, and 2.0% in this order.

Zn²⁺Is used for improving the refractive index of the glass, improving the thermal stability of the glass and reducing the liquid by proper introductionPhase temperature and glass transition temperature. However, if Zn is introduced excessively²⁺The low dispersion property is seriously impaired and the chemical durability of the glass is deteriorated. Thus, in the optical glass of the present invention, Zn²⁺The upper limit of the content of (b) is preferably 15%, and more preferably 13%, 12%, 10%, and 9% in this order. In addition, Zn²⁺When the amount of (2) is too small, the liquidus temperature and the glass transition temperature tend to be high. Thus, Zn²⁺The lower limit of the content of (b) is preferably 0%, and more preferably 0.5%, 1.0%, 2.0%, and 3.0% in this order.

In the optical glass of the present invention, other than Ba²⁺In addition, contains a compound selected from Mg²⁺、Ca²⁺、Zn²⁺And Sr²⁺1 or more of (2) as a divalent component. In this case, Mg is added to the glass from the viewpoint of improving the weather resistance of the glass and obtaining desired optical properties²⁺、Ca²⁺、Zn²⁺、Sr²⁺And Ba²⁺Total content of (1), (2) R2 ═ Mg²⁺+Ca²⁺+Zn²⁺+Sr²⁺+Ba²⁺]The upper limit of (b) is preferably 53%, and more preferably 50%, 47%, 45%, and 43% in this order. The lower limit of the total content R2 is preferably 25%, and more preferably 28%, 31%, 33%, and 35% in this order.

In the optical glass of the present invention, Ba is used from the viewpoint of improving the refractive index and improving the thermal stability of the glass at the same time²⁺In a content relative to Mg²⁺、Ca²⁺、Zn²⁺And Sr²⁺The proportion of the total content of (A): cation ratio alpha 2[ Ba ]²⁺/(Mg²⁺+Ca²⁺+Zn² ⁺+Sr²⁺)]Is 1.50 or less. The upper limit of the cation ratio α 2 is preferably 1.4, and more preferably 1.2, 1.1, and 1.0 in this order. From the viewpoint of improving the weather resistance of the glass, the cation ratio α 2 is preferably more than 0, and the lower limit of the cation ratio α 2 is preferably in the order of 0.1, 0.2, 0.3, 0.5, and 0.6. By satisfying such conditions, Ba²⁺The content of (B) is not significantly excessive relative to the content of other divalent components, so that the content of Ba derived from Ba can be suppressed²⁺Precipitation of crystals of (4). Therefore, Ba is blended in such a well-balanced manner²⁺And other divalent components, even if the refractive index is increased and the number of components forming a mesh structure is decreased, the thermal stability of the glass can be improved.

In the optical glass of the present invention in which the cation ratio α 2 is 1.50 or less, the temperature difference between the crystallization peak temperature Tc) and the glass transition temperature Tg (Tc-Tg) is large, and Tc-Tg is 150 ℃ or more. When the cation ratio α 2 is set to be within the above range, Tc — Tg increases, and when the glass is re-softened, the glass can be softened at a temperature lower than Tc, so that the glass does not crystallize, and the thermal stability of the glass can be improved.

Further, from the viewpoint of improving the thermal stability of the glass, Ba²⁺In a content relative to Mg²⁺And Sr²⁺The proportion of the total content of (A): cation ratio [ Ba ]²⁺/(Mg²⁺+Sr²⁺)]The upper limit of (b) is preferably 3.0, and more preferably 2.5, 2.0, 1.8 and 1.7 in this order. In addition, cation ratio [ Ba ]²⁺/(Mg²⁺+Sr²⁺)]The lower limit of (b) is preferably 0.3, and more preferably 0.5, 0.7, and 0.8 in this order.

In addition, from the viewpoint of improving the thermal stability of the glass and obtaining desired optical characteristics, Sr²⁺And Ba²⁺Total content of (A) relative to Mg²⁺And Ca²⁺The proportion of the total content of (A): cation ratio [ (Sr)²⁺+Ba²⁺)/(Mg²⁺+Ca²⁺)]The upper limit of (b) is preferably 3.0, and more preferably 2.5, 2.0, 1.8 and 1.7 in this order. In addition, the cation ratio [ (Sr)²⁺+Ba²⁺)/(Mg²⁺+Ca²⁺)]The lower limit of (b) is preferably 0.3, and more preferably 0.5, 0.7, 0.8, and 1.0 in this order.

It is to be noted that Mg is substituted by²⁺、Ca²⁺、Zn²⁺、Sr²⁺And Ba²⁺Among the divalent components of the composition, Ba²⁺The refractive index and weather resistance of the glass can be effectively improved, but excessive introduction significantly impairs the thermal stability of the glass. On the other hand, Zn²⁺Improved glassThe thermal stability of glass is greatly impaired by excessive introduction of the glass. Then, from the viewpoint of obtaining the thermal stability and desired optical constants of the glass, Zn²⁺Relative to the content of Ba²⁺The content ratio of (A): cation ratio [ Zn ]²⁺/Ba²⁺]The upper limit of (b) is preferably 0.60, and more preferably 0.55 and 0.50 in this order. In addition, cation ratio [ Zn ]²⁺/Ba²⁺]The lower limit of (b) is preferably 0.10, and more preferably 0.15, 0.20, and 0.25 in this order.

Gd³⁺、Y³⁺、La³⁺And Yb³⁺All of them are components contributing to improvement in the weather resistance of the glass and increase in the refractive index. However, if these components are excessively introduced, thermal stability and homogeneity of the glass may be deteriorated, and low dispersion properties may be significantly impaired. Thus, in the optical glass of the present invention, Gd³⁺The upper limit of the content of (b) is preferably 13%, more preferably 10%, 7%, 5%, 4% in this order. In addition, Gd³⁺The lower limit of the content of (b) is preferably 0%, and more preferably 0.5%, 1.0%, and 2.0% in this order. Y is³⁺The upper limit of the content of (b) is preferably 10%, and more preferably 7.0%, 5.0%, 4.0%, and 3.0% in this order. In addition, Y³⁺The lower limit of the content of (b) is preferably 0%, and more preferably 0.5% and 1.0%. La³⁺The upper limit of the content of (b) is preferably 10%, and more preferably 7.0%, 5.0%, 3.0%, and 2.0% in this order. In addition, La³⁺The lower limit of the content of (b) is preferably 0%, more preferably 0.05%. Yb of³⁺The upper limit of the content of (b) is preferably 5.0%, and more preferably 3.0%, 2.0%, 1.5%, and 1.0%. In addition, Yb³⁺The lower limit of the content of (b) is preferably 0%, more preferably 0.05%. Yb is to be noted³ ⁺Since the near infrared region has an absorption property, when light in the near infrared region is used, it is preferable not to introduce Yb³⁺。

In view of effectively increasing the refractive index, Gd is preferably used³⁺、Y³⁺、La³⁺And Yb³⁺Such rare earth elements are appropriately introduced. Thus, it is possible to provideThe optical glass of the present invention contains Gd³⁺、Y³⁺、La³⁺And Yb³⁺Any 1 or more of (a). However, if these components are introduced excessively, the following tendency is present: the thermal stability of the glass is deteriorated and the low dispersion property is remarkably impaired. Then, Gd³⁺、Y³⁺、La³⁺And Yb³⁺Total content of Re2 ═ Gd³⁺+Y³⁺+La³⁺+Yb³⁺]The upper limit of (b) is preferably 5.0%, and more preferably 4.5%, 4.0%, and 3.5% in this order. The lower limit of the total content Re2 is preferably 0.1%, and more preferably 0.2%, 0.4%, 1.0%, 1.5%, and 2.0%. When 2 or more kinds of rare earth elements are introduced more than the single rare earth element, the thermal stability of the glass may be improved. Therefore, the optical glass of the present invention preferably contains Gd³⁺、Y³⁺、La³And Yb³⁺Any 2 or more rare earth elements.

In the optical glass of the present invention, P is added so that the cation ratio α 2 is within a predetermined range, and the thermal stability of the glass is ensured and the refractive index is effectively increased⁵⁺、B³⁺And Al³⁺The ratio of the total content of (a) to the total content of rare earth elements Re 2: cation ratio beta 2[ (P)⁵⁺+B³⁺+Al³⁺)/Re2]Is 14.0 or more. The lower limit of the cation ratio β 2 is preferably 14.1, and further preferably 14.2, 14.4, 14.6, 14.8, and 15.0 in this order. The upper limit of the cation ratio β 2 is preferably 120.0, and more preferably 90.0, 70.0, 50.0, 40.0, 30.0, and 20.0 in this order.

In the present invention, the cation ratio α 2 and the cation ratio β 2 are closely related from the viewpoint of obtaining desired optical characteristics and improving the thermal stability of the glass. This will be explained below.

Since rare earth elements are effective for increasing the refractive index of the glass, there is a possibility that the thermal stability is impaired by excessive introduction of rare earth elements, it is preferable to increase the thermal stability of the glass and reduce the total content of rare earth elements Re2 in the optical glass of the present invention. Specifically, the total content Re2 of rare earth elements that is the denominator of the cation ratio β 2 is suppressed, and the composition is adjusted so that the cation ratio β 2 is 14.0 or more, thereby improving the thermal stability.

On the other hand, the thermal stability of the glass is improved by limiting the cation ratio β 2 to a predetermined range, but the refractive index is lowered in accordance with the decrease in the total content Re2 of the rare earth element. Thus, in the optical glass of the present invention, Ba is added²⁺More lead-in amount of (B), thereby effectively embodying Ba²⁺The effect of (a) to achieve an increase in refractive index. However, if Ba²⁺Relative to Mg²⁺、Ca²⁺、Zn²⁺And Sr²⁺The upper limit of the cation ratio α 2 (the cation ratio α 2 is 1.50 or less) is limited in the present invention because the introduction of the total content of (a) is too large and the thermal stability is rather impaired.

By adjusting the glass composition so that the cation ratio α 2 and the cation ratio β 2 fall within the predetermined ranges in this manner, desired optical characteristics can be obtained and the thermal stability of the glass can be improved.

Si⁴⁺Is an effective component for improving chemical durability while maintaining low dispersibility. However, if the amount of the compound to be introduced is too large, the following tendency is present: the glass transition temperature and the sag temperature increase and the refractive index decreases. Thus, in the optical glass of the present invention, Si⁴⁺The upper limit of the content of (b) is preferably 3.0%, and more preferably 2.0%, 1.5%, 1.0%, and 0.5% in this order. In addition, Si⁴⁺And P⁵⁺、B³⁺、Al³⁺Are network components, but it is not necessary to introduce Si into the optical glass of the present invention⁴⁺。

Li⁺Is an effective component for lowering the glass transition temperature, the sag temperature, and the dispersion. In particular, P is used for the purpose of reducing the dispersion of the glass⁵⁺、B³⁺And Li⁺Coexistence is very efficient. However, if Li is excessively introduced⁺The glass tends to have poor chemical durability (weather resistance, alkali resistance, etc.) and a sharply decreased refractive index. Thus, the light of the present inventionIn the glass, Li⁺The upper limit of the content of (b) is preferably 26%, and more preferably 23%, 20%, 17%, 15%, 10%, 8%, 5%, and 3% in this order. In addition, Li⁺The lower limit of the content of (b) is preferably 0%, and the smaller the content is, the more preferably 0.1%, 1.0%, 1.5%, 2.0%, 2.5%. In the case of manufacturing an optical element by the reheat press molding method, substantially no Li can be introduced⁺。

Na⁺And K⁺All are optional components introduced for the purpose of improving the devitrification resistance of the glass, lowering the glass transition temperature, sag temperature, liquidus temperature, and improving the meltability of the glass. Appropriate amount of Na⁺And K⁺The introduction of (2) can improve the stability of the glass and involves lowering the liquidus temperature and the transition temperature, but if the introduction is excessive, the chemical durability is significantly deteriorated and the refractive index tends to be lowered. Thus, in the optical glass of the present invention, Na⁺And K⁺The upper limit of the content of (b) is preferably 8.0%, and more preferably 5.0%, 4.0%, and 3.0%, respectively. It is particularly preferable that Na is not substantially introduced⁺And K⁺。

If Li⁺、Na⁺And K⁺When the total content of (b) is too small, the glass transition temperature and the sag temperature increase, and the meltability deteriorates. Therefore, in the optical glass of the present invention, Li⁺、Na⁺And K⁺Total content R of₂2＝[Li⁺+Na⁺+K⁺]The upper limit of (b) is preferably 26%, and more preferably 23%, 20%, 17%, 15%, 10%, 8%, 5% in this order. In addition, the total content R₂The lower limit of 2 is preferably 0%, and the smaller the lower limit is more preferably 0.5%, 1.0%, 1.5%, 2.0%, 3.0%. In the case of producing an optical element by the reheat press molding method, Li is used⁺、Na⁺And K⁺Total content R of₂2 is preferably 10.0% or less, more preferably 5.0% or less, more preferably 3% or less, further preferably 2% or less, further preferably 1% or less, and particularly preferably substantially none of them is introduced.

In the optical glass of the present invention, Cs as an alkali metal component⁺The introduction of (b) is not necessarily essential, but rather undesirable because it is disadvantageous in view of the cost of raw materials. In addition, Cs⁺Since the refractive index is lowered and the weather resistance is remarkably impaired, it is preferable not to introduce Cs⁺。

In view of both meltability and thermal stability of glass, P is⁵⁺The content being relative to the total content R of the alkali metal component₂2: cation ratio [ P ]⁵⁺/R₂2]The upper limit of (b) is preferably 50, and more preferably 40, 30, 25, 20, 15, and 10. In addition, the cation ratio [ P ]⁵⁺/R₂2]The lower limit of (b) is preferably 1.0, and more preferably 1.2, 1.5, 1.8 and 2.0 in this order.

The optical glass of the present invention may contain F, which is a halogen^-、Cl^-、Br^-、I^-As an arbitrary component. The content may be in the anion fraction of anions (e.g. [ F ]^-/(O^2-+F^-)]) And (4) showing. F^-The upper limit of the content of (b) is preferably 7%, and more preferably 5%, 3%, 2%, 1%, 0.5%, and 0.1% in this order. In addition, Cl^-、Br^-、I^-The upper limit of the content of (b) is preferably 5%, and more preferably 3%, 2%, 1%, 0.5%, and 0.1% in this order. When the glass contains a halogen, it is preferable to suppress volatilization of the glass by using B in the glass³⁺The upper limit of (b) is 15%, preferably 10%, 5%, 3%, 1%, and most preferably substantially not contained. However, the halogen content is not limited to 1% or less. In particular, it is preferable that the glass contains substantially no halogen in order to suppress volatilization of components from the glass and improve homogeneity of the glass.

The optical glass of the present invention may contain W⁶⁺、Ti⁴⁺、Bi³⁺And Nb⁵⁺Form a simpleThe reduced component is an arbitrary component. These easily reducible components are effective components for increasing the refractive index. However, W⁶⁺、Ti⁴⁺、Bi³⁺And Nb⁵⁺The Abbe number (vd) of the glass is significantly reduced. Then, the total content [ W ] of the above-mentioned easily reducible component⁶⁺+Ti⁴⁺+Bi³⁺+Nb⁵⁺]The upper limit of (b) is preferably 4.0%, and more preferably 3.0%, 2.0%, 1.0%, and 0.5% in this order. It is particularly preferable that the above-mentioned easily reducible component is not substantially introduced.

The optical glass of the present invention as described above is preferably substantially composed of a glass selected from the group consisting of P⁵⁺、B³⁺、Si⁴⁺、Al³⁺、Li⁺、Na⁺、K⁺、Mg² ⁺、Ca²⁺、Zn²⁺、Sr²⁺、Ba²⁺、Gd³⁺、Y³⁺、La³⁺And Yb³⁺The composition of (a). Total content of these components [ P⁵⁺+B³⁺+Si⁴⁺+Al³ ⁺+Li⁺+Na⁺+K⁺+Mg²⁺+Ca²⁺+Zn²⁺+Sr²⁺+Ba²⁺+Gd³⁺+Y³⁺+La³⁺+Yb³⁺]Preferably 95% or more, more preferably 98% or more, more preferably 99% or more, and still more preferably 100%.

The phrase "substantially not contained" means that the content may be less than 0.2% on the basis. Since the substantially non-contained component or additive is preferably not contained in the glass, the content thereof is preferably less than 0.1%, more preferably less than 0.08%, still more preferably less than 0.05%, still more preferably less than 0.01%, and still more preferably less than 0.005%.

When the optical glass of the present invention is composed of the above components and the total amount is 100% by mass, the optical glass may beIntroducing Sb in an amount of 4 mass% or less in an external manner₂O₃、SnO₂、CeO₂And the like. Sb₂O₃The upper limit of the content of (b) is preferably 4% by mass, and more preferably 3% by mass, 2% by mass, 1% by mass, 0.5% by mass, and 0.1% by mass in this order. In addition, Sb₂O₃The lower limit of the content of (b) is preferably 0%, and more preferably 0.01%, 0.02%, and 0.04% by mass in this order. Further, SnO₂、CeO₂Since the water vapor permeability of glass may be deteriorated, it is preferably introduced in an amount of 1 mass% or less, and particularly preferably not substantially introduced.

In embodiment 2, the glass composition of the optical glass has been described as being expressed mainly in terms of cation%, but the analytical values obtained by quantitative analysis of each component by ICP-AES analysis or the like can be expressed in terms of cation% by the following method.

As a result of quantitative analysis of the glass composition, the content of the cationic element in the glass component composed of cations and anions may be expressed as a percentage of atomic%. Such composition can be expressed in terms of cation% in the present invention by the following method, for example.

That is, the molar percentage of each cation is determined by dividing the content (atomic%) of each cation of the glass component after quantitative determination by the specific atomic weight, and the ratio of the anion to be determined to all the cations contained is expressed as molar percentage, and is expressed in terms of cation%.

For example, the content (atomic%) of n cations is quantified as m by quantitative analysis₁,m₂,…,m_i,…,m_nEach cation having an atomic weight of M₁,M₂,…,M_i,…,M_nWhen 1 component (m)_i,M_i) The cation content (cation%) of (c) can be determined by the following equation.

[(m_i/M_i)/{(m₁/M₁)+(m₂/M₂)+…+(m_i/M_i)+…+(m_n/M_n)}]×100

The content (atomic%) of the anion element may be quantified by quantitative analysis, but the same principle as described above may be used in terms of the anion content (anion%) in the anion.

As a result of quantitative analysis of the glass composition, the glass component may be expressed on an oxide basis, and the content of the glass component may be expressed in mass%. The expression of such a composition can be expressed in terms of cation% by the following method, for example.

The oxide composed of the cation A and oxygen is labeled "A_mO_n". m and each is an integer determined by stoichiometry. For example, B³⁺In the case of (2), the label based on oxide reference is B₂O₃，m＝2、n＝3，Si⁴⁺In the case of (2), is SiO₂，m＝1、n＝2。

First, A will be expressed in mass%_mO_nIs divided by A_mO_nFurther multiplied by m. This value was defined as Q. Then, Q is summed up for all the glass components. Assuming that the total value of Q is Σ Q, the values of Q of the respective glass components are normalized so that Σ Q is 100%, and the obtained value is As represented by cation%⁺The content of (a). S is 2 n/m.

The characteristics (optical characteristics, thermal stability) of the optical glass of the present embodiment are the same as those described in embodiment 1. Therefore, the description is omitted in this embodiment.

Production of optical glass

The optical glass of the present invention can be produced by mixing the raw materials to have the above-mentioned predetermined composition and by a known glass production method.

The raw materials (glass raw materials) of the respective components in the glass are not particularly limited, and oxides, carbonates, nitrates, hydroxides, and the like of the respective metals can be mentioned.

Manufacture of optical elements and the like

In order to produce an optical element using the optical glass of the present invention, a known method may be applied. For example, the optical glass of the present invention is melted, a plate-shaped glass material is molded, and the plate-shaped glass material is finely divided into a predetermined volume to produce a glass material for press molding. Alternatively, a glass material for press molding is produced by continuously molding a glass gob having a predetermined volume from a state in which the optical glass of the present invention is melted. Then, the glass material is reheated and press-molded (reheat press-molding) to produce an optical element blank. Further, the optical element blank is processed by a process including polishing to produce an optical element or a glass material for precision press molding.

Alternatively, an optical element is produced by hot forming molten glass to produce a glass material (preform) for precision press molding, and heating and precision press molding the glass material.

Alternatively, an optical element is produced by directly molding (direct press molding) molten glass to produce a glass molded body, and polishing the molded body.

The optically functional surface of the optical element thus produced is coated with an antireflection film, a total reflection film, or the like depending on the purpose of use.

Examples of the optical element include various lenses such as a spherical lens, an aspherical lens, a microlens, and a lens array, a prism, and a diffraction grating.

While the embodiments of the present invention have been described above, the present invention is not limited to these embodiments at all, and can be implemented in various ways without departing from the scope of the present invention.

Examples

The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

(example 1A and comparative example 1A)

Tables 1 to 5 show optical glasses (samples 1A to 50A) of examples according to embodiment 1 of the present invention, and table 6 shows an optical glass (sample ref1A) of a comparative example of the present invention. Samples 2A and 19A shown in table 6 are the same as those shown in tables 1 and 2, and are described together for comparison of examples and comparative examples.

These optical glasses were produced by the following procedure and subjected to various evaluations. The results are shown in tables 1 to 6.

[ production of optical glass ]

First, oxides, hydroxides, carbonates, and nitrates corresponding to the constituent components of the glass were prepared as raw materials, and the raw materials were weighed and prepared so that the glass composition of the obtained optical glass had each composition shown in each table, and the raw materials were thoroughly mixed. The prepared raw materials (batch raw materials) thus obtained were put into a platinum crucible, melted and stirred in an electric furnace at a temperature range of 1200 to 1400 ℃ depending on the meltability of the raw materials to homogenize the raw materials, clarified, and then the molten glass was poured out through a pouring nozzle and cast into a mold preheated to an appropriate temperature. The cast glass was put into a slow cooling furnace and cooled to room temperature according to a predetermined slow cooling schedule to obtain each optical glass.

[ evaluation of optical glass ]

The obtained optical glass was subjected to confirmation of glass composition, evaluation of refractive index (nd), abbe number (vd), glass transition temperature (Tg), crystallization start temperature (Tx), crystallization peak temperature (Tc), and presence or absence of internal crystal by the following methods. In addition, the crystallization peak intensity (Δ) was also measured for some samples, and the weather resistance (D) was also measured_H) And (4) testing.

[1] Confirmation of glass composition

Appropriate amounts of the optical glasses obtained as described above were collected, subjected to acid and alkali treatments, and the contents of the respective components were determined by inductively coupled plasma mass spectrometry (ICP-AES method), and it was confirmed that the respective optical glasses were consistent with the oxide compositions of the respective samples shown in the respective tables.

[2] Refractive index (nd) and Abbe number (vd)

The optical glass cooled to room temperature was again held at a temperature between the glass transition temperature (Tg) and the sag temperature (Ts) by a refractometry method standardized by japan optical nitre industrial association, and the temperature was decreased at a temperature decrease rate of-30 ℃/hour to remove distortion (distortion) in the glass, and the refractive index (nd) and abbe number (vd) ("GMR-1" manufactured and sold by shimadzu Device, ltd.) were measured with respect to the optical glass thus obtained.

[3] Glass transition temperature (Tg), crystallization peak temperature (Tc) and peak intensity (delta)

The temperature was measured by a differential scanning calorimeter manufactured by Bruker AXS at a temperature rise rate of 10 ℃ per minute. Further, a temperature difference (Tc-Tg) was calculated from the measured Tg and Tc. The peak intensity (Δ) is calculated based on the differential scanning calorimeter showing the differential travel heat curve.

[4] Presence or absence of internal crystallization

Casting (cast) glass from a molten state to a mold in an atmosphere to produce a glass molded body having a flat free surface on the upper surface, and cutting the glass molded body to obtain a glass molded body of 1X 1cm³The cubic glass sample of (1). This glass sample was charged into a heating furnace, kept at the temperature Tg for 10 minutes (primary heating), then kept at the temperature at which the glass softens (Tp) for 10 minutes (secondary heating), and then taken out of the heating furnace and left to cool. Next, the glass sample was polished, and the presence or absence of internal crystals in the glass was observed from the polished surface with a microscope. From this observation, the case where no crystal having a diameter of 0.1 μm or more is present was evaluated as "no crystal", and the case where crystal having a diameter of 0.1 μm or more is present was evaluated as "crystal present". The temperature Tp varies among samples, but softening of all samples was confirmed at a temperature in the range of (Tg + about 130 ℃) to (Tg + about 180 ℃).

[5]Weather resistance (D)_H) Test of

The optical glass thus obtained was molded into a glass sample (30X 3mm) having a main surface subjected to surface polishing according to JOGIS07 standard by the Japan optical glass society, and treated under a temperature cycle environment of high temperature and high humidity for 48 hours. Then, the haze value of the glass sample was measured using a haze meter (TC-HIIIDPK) manufactured by tokyo electrochromism (some cases). The haze value can be determined by the scattered light intensity/transmitted light intensity × 100 (unit:%). The results are described below.

As shown in tables 1 to 5, the optical glasses (samples 1A to 50A) of the examples of the present invention were the following glasses: a refractive index nd of 1.625-1.680, an Abbe number vd of 58-65, and a mass ratio [ P [ ]₂O₅/B₂O₃]And a mass ratio of alpha 1[ BaO/(MgO + CaO + ZnO + SrO ]]And mass ratio beta 1[ (P)₂O₅+B₂O₃+Al₂O₃)/Re1]Within the desired range ([ P ]₂O₅/B₂O₃]More than 1 to 15.0, a mass ratio α 1 of 3.0 or less, and a mass ratio β 1 of 4.80 or more).

In the optical glass of the present example, the average value of the temperature difference (Tc-Tg) between the temperature Tg and the temperature Tc was about 185 ℃, and it was confirmed that the temperature Tp of any sample was lower than the crystallization peak temperature Tc (i.e., in the relationship of Tp < Tc), and that the glass after solidification had not undergone internal crystallization and had high thermal stability.

In particular, the following were confirmed for sample 19A in tables 2 and 6: among the samples 1A to 50A, the sample having the smallest temperature difference (Tc-Tg) exhibited no internal crystallization and high thermal stability.

In addition, the following were confirmed for sample 2A in tables 1 and 6: from the viewpoint of the refractive index and Abbe number, the temperature difference (Tc-Tg) was 178 ℃ even in the sample ref1A (comparative example) very close to Table 6, and internal crystallization did not occur, and the thermal stability was high as in the other samples.

In contrast, sample ref1A in Table 6, which is an optical glass of a comparative example of the present invention, had a temperature difference (Tc-Tg) of 139 ℃ and was softened at a temperature Tp (710 ℃) which was much higher than the crystallization peak temperature Tc (667 ℃). That is, the temperature Tp and the temperature Tc of the sample ref1A are in the relationship Tp > Tc. Further, it was confirmed that internal crystallization occurred in the glass of sample ref1A after solidification, and thermal stability was poor.

The reason for the difference is as follows: the mass ratio α 1 of the sample ref1A in table 6 as an optical glass of the comparative example was 3.0 or less, but the mass ratio β 1 as an index of thermal stability of the glass was not within a predetermined range (4.80 or more).

As described above, the temperature difference (Tc-Tg) of the optical glass of the example of the present invention is sufficiently large. Therefore, the glass can be surely softened at a temperature Tp lower than the temperature Tc. Therefore, the optical glass of the present invention can be suitably used for reheat press molding in which precise temperature control is difficult.

On the other hand, since the optical glass of comparative example (sample ref1A in table 6) has a small temperature difference (Tc-Tg) and the softening temperature Tp is higher than the crystallization peak temperature Tc, internal crystals are generated when the optical glass of comparative example is softened, and it is difficult to apply the optical glass of comparative example to reheat press molding.

Further, with respect to weather resistance (D)_H) As a result of the test, it was confirmed that the optical glass of the present example (sample 2A in tables 1 and 6) was excellent in transparency without surface deterioration after being treated at high temperature and high humidity for a long time. In addition, the haze value was 0.1%.

From these results, it was confirmed that the optical glass of the present invention has excellent weather resistance.

Example 1B and comparative example 1B

Tables 7 to 10 show optical glasses (samples 1B to 47B) of examples according to embodiment 2 of the present invention, and table 11 shows an optical glass (sample ref1B) of a comparative example of the present invention. Samples 16B and 25B shown in table 11 are the same as those shown in table 8, and are described together for comparison of examples and comparative examples.

These optical glasses were produced by the same procedure as in example 1A and comparative example 1B, and subjected to various evaluations as described above. The results are shown in tables 7 to 11.

As shown in tables 7 to 11, the optical glasses (samples 1B to 47B) of the examples of the present invention were the following glasses: refractive index nd of 1.625 ℃ -1.680 Abbe number vd ranging from 58 to 65, especially, cation ratio [ P ]⁵⁺/B³⁺]Cation ratio alpha 2[ Ba ]²⁺/(Mg²⁺+Ca²⁺+Zn²⁺+Sr²⁺)]And cation ratio beta 2[ (P)⁵⁺+B³⁺+Al³⁺)/Re2]In the desired range (cation ratio [ P ]⁵⁺/B³⁺]More than 1 to 10.0, a cation ratio of alpha 2/1.50 or less, and a cation ratio of beta 2 of 14.0 or more).

In the optical glass of the present example, the average value of the temperature difference (Tc-Tg) between the temperature Tg and the temperature Tc was about 185 ℃, and it was confirmed that the temperature Tp of any sample was lower than the crystallization peak temperature Tc (i.e., in the relationship of Tp < Tc), and that the glass after solidification had no internal crystallization and had high thermal stability.

In particular, the following were confirmed for sample 16B in table 8 and table 11: among samples 1B to 47B, the sample having the smallest temperature difference (Tc-Tg) exhibited no internal crystallization and high thermal stability.

In addition, the following were confirmed for sample 25B in table 8 and table 11: from the viewpoint of the refractive index and Abbe number, the temperature difference (Tc-Tg) was 178 ℃ even in the sample ref1B (comparative example) very close to Table 11, and internal crystallization did not occur, and the thermal stability was high as in the other samples.

In contrast, sample ref1B in Table 11, which is an optical glass of a comparative example of the present invention, had a temperature difference (Tc-Tg) of 139 ℃ and was softened at a temperature Tp (710 ℃) which was much higher than the crystallization peak temperature Tc (667 ℃). That is, the temperature Tp and the temperature Tc of the sample ref1B are in the relationship Tp > Tc. Further, it was confirmed that internal crystallization occurred in the glass of sample ref1B after solidification, and thermal stability was poor.

The reason for the difference is as follows: the sample ref1B in table 11 as the optical glass of the comparative example had a cation ratio α 2 of 1.50 or less, but the cation ratio β 2 as an index of thermal stability of the glass was not within a predetermined range (14.0 or more).

On the other hand, since the optical glass of comparative example (sample ref1B in table 11) has a small temperature difference (Tc-Tg) and the softening temperature Tp is higher than the crystallization peak temperature Tc, internal crystals are generated when the optical glass of comparative example is softened, and it is difficult to apply the optical glass of comparative example to reheat press molding.

Further, with respect to weather resistance (D)_H) As a result of the test, it was confirmed that the optical glass of the present example (sample 25B in table 8 and table 11) was excellent in transparency without surface deterioration after being treated at high temperature and high humidity for a long time. In addition, the haze value was 0.1%.

(example 2)

Optical lenses were produced using the optical glasses (samples 1A to 50A and samples 1B to 47B) produced in example 1A and example 1B. Specifically, each of the optical glasses of example 1A and example 1B was processed into a predetermined shape to prepare an optical glass material. Next, the optical glass material is heated and softened, press-molded into a shape similar to a desired lens shape, and after press-molding, the glass is subjected to blunting (annealing), and is finished into an optical lens by a processing step including a polishing step. In addition, a known method may be appropriately applied to the press molding method, annealing method, and processing step of glass.

The optical lens thus obtained was confirmed to have the following: even when the glass is heated at a relatively high temperature during the reheat press molding, the glass does not crystallize, and a good optical lens can be obtained.

Comparative example 2

By using the optical glasses produced in comparative examples 1A and B (sample ref1A in table 6 and sample ref1B in table 11) in the same manner as in example 2, the production of an optical lens was attempted.

However, the following were confirmed in the optical glass of the comparative example: the optical lens obtained has low thermal stability, and is internally crystallized by heating during reheat press molding.

The present invention is summarized below.

As shown in tables 1 to 5, the optical glasses (samples 1A to 50A) of embodiment 1 are P₂O₅、B₂O₃And Al₂O₃Total content of [ P ]₂O₅+B₂O₃+Al₂O₃]55 mass% or less of glass satisfying the following conditions:

the optical glass comprises BaO,

Any 1 or more selected from MgO, CaO, ZnO and SrO, and

the refractive index nd is 1.625-1.680, and the Abbe number vd is 58-65.

Further, the optical glass of embodiment 1 satisfies Gd₂O₃、Y₂O₃、La₂O₃And Yb₂O₃Total content of [ Gd ]₂O₃+Y₂O₃+La₂O₃+Yb₂O₃]0.5 to 11% by mass.

Further, the optical glass of embodiment 1 is preferably P₂O₅The content of (B) is 25 to 43 mass%.

In addition, the optical glass of embodiment 1 preferably contains BaO in an amount of 15 to 45 mass%.

In the optical glass of embodiment 1, the mass ratio of the content of ZnO to the content of BaO [ ZnO/BaO ] is preferably 0.10 to 0.33.

In addition, the optical glass of embodiment 1 is preferably Li₂The content of O is0 to 2.0 mass%.

From another viewpoint, the optical element is composed of the optical glass of embodiment 1.

From another viewpoint, the optical glass material is composed of the optical glass of embodiment 1.

On the other hand, the optical glass (samples 1A to 50A) of embodiment 1 is P₂O₅、B₂O₃And Al₂O₃Total content of [ P ]₂O₅+B₂O₃+Al₂O₃]55 mass% or less of glass satisfying the following conditions:

the optical glass comprises BaO,

Any 1 or more selected from MgO, CaO, ZnO and SrO, and

the content of ZnO is 15 mass% or less,

the refractive index nd is 1.625-1.680, and the Abbe number vd is 58-65.

As shown in tables 7 to 10, the optical glasses (samples 1B to 47B) of embodiment 2 were P⁵⁺、B³⁺And Al³⁺Total content of [ P ]⁵⁺+B³⁺+Al³⁺]Glass of 65 cation% or less, which satisfies the following conditions:

the optical glass contains Ba²⁺、

Selected from Mg²⁺、Ca²⁺、Zn²⁺And Sr²⁺Any 1 or more of, and

the refractive index nd is 1.625-1.680, and the Abbe number vd is 58-65.

Further, the optical glass of embodiment 2 satisfies Gd³⁺、Y³⁺、La³⁺And Yb³⁺Total content of [ Gd ]³⁺+Y³ ⁺+La³⁺+Yb³⁺]0.1 to 5.0 cation%.

Further, the optical glass of embodiment 2 is preferably P⁵⁺、B³⁺And Al³⁺Total content of [ P ]⁵⁺+B³⁺+Al³⁺]49 to 65 cation%.

Further, the optical glass of embodiment 2 is preferably P⁵⁺The content of (A) is 20-50 cation%.

In addition, the optical glass of embodiment 2 is preferably Ba²⁺The content of (A) is 5-30 cation%.

In addition, the optical glass of embodiment 2 is preferably Zn²⁺Relative to the content of Ba²⁺Cation ratio of contents [ Zn ]²⁺/Ba²⁺]0.10 to 0.60.

In addition, in the optical glass of embodiment 2, the cation ratio β 2 is preferably 14.1 to 120.0.

In addition, the optical glass of embodiment 2 is preferably Li⁺The content of (B) is 0-10.0 cation%.

From another viewpoint, the optical element is composed of the optical glass of embodiment 2.

From another viewpoint, the optical glass material is composed of the optical glass of embodiment 2.

On the other hand, the optical glass (samples 1B to 47B) of embodiment 2 is P⁵⁺、B³⁺And Al³⁺Total content of [ P ]⁵⁺+B³⁺+Al³⁺]Glass of 65 cation% or less, which satisfies the following conditions:

the optical glass contains Ba²⁺、

Selected from Mg²⁺、Ca²⁺、Zn²⁺And Sr²⁺Any 1 or more of, and

Zn²⁺the content of (A) is 15 cation% or less,

the refractive index nd is 1.625-1.680, and the Abbe number vd is 58-65.

Description of the symbols

Tg glass transition temperature

Peak temperature of Tk endotherm

Tx crystallization onset temperature

Tc peak crystallization temperature

Absolute value of heat difference between ATk and Tg

Absolute value of heat difference between B Tx and Tc

Claims

1. An optical glass which is P₂O₅、B₂O₃And Al₂O₃Total content of [ P ]₂O₅+B₂O₃+Al₂O₃]Glass is 42 mass% or less, wherein,

the optical glass comprises:

BaO、

any 1 or more selected from MgO, CaO, ZnO and SrO, and

P₂O₅of (1) containsThe amount is 25 to 37% by mass,

Gd₂O₃the content of (B) is 0.1 mass% or more,

the mass ratio alpha 1[ BaO/(MgO + CaO + ZnO + SrO) ] of the content of BaO to the total content of MgO, CaO, ZnO and SrO is 2.8 or less,

P₂O₅、B₂O₃and Al₂O₃Relative to Gd₂O₃、Y₂O₃、La₂O₃And Yb₂O₃The mass ratio of the total content of (1) (. beta.1 [ (P)₂O₅+B₂O₃+Al₂O₃)/(Gd₂O₃+Y₂O₃+La₂O₃+Yb₂O₃)]Is in the range of 4.80 to 6.53,

BaO and P₂O₅Total content of [ BaO + P ]₂O₅]Is not more than 75% by mass of a polymer,

the refractive index nd is 1.630 to 1.680, and the Abbe number vd is 58 to 65.

2. The optical glass according to claim 1, wherein the MgO content is 2.64 mass% or more.

3. The optical glass according to claim 1, wherein the content of ZnO is 7.10% by mass or more.

4. An optical glass which is P⁵⁺、B³⁺And Al³⁺Total content of [ P ]⁵⁺+B³⁺+Al³⁺]Is a glass having a content of 56 cation% or less, wherein,

the optical glass comprises:

Ba²⁺、

selected from Mg²⁺、Ca²⁺、Zn²⁺And Sr²⁺Any 1 or more of, and

P⁵⁺the content of (A) is 20 to 40 positive ions,

Gd³⁺the content of (A) is more than 0.5 cation percent,

Ba²⁺in a content relative to Mg²⁺、Ca²⁺、Zn²⁺And Sr²⁺Cation ratio of total content of alpha 2[ Ba ]²⁺/(Mg²⁺+Ca²⁺+Zn²⁺+Sr²⁺)]The content of the organic acid is less than 1.0,

P⁵⁺、B³⁺and Al³⁺Relative to Gd³⁺、Y³⁺、La³⁺And Yb³⁺The cation ratio of the total content of beta 2[ (P)⁵⁺+B³⁺+Al³⁺)/(Gd³⁺+Y³⁺+La³⁺+Yb³⁺)]Is in the range of 14.0 to 37.43 inclusive,

Ba²⁺and P⁵⁺Total content of [ Ba ]²⁺+P⁵⁺]The content of the cationic polymer is less than 65 cation percent,

the refractive index nd is 1.630 to 1.680, and the Abbe number vd is 58 to 65.

5. The optical glass of claim 4, wherein Mg²⁺The content of (A) is 5.26 cation% or more.

6. The optical glass as claimed in claim 4, wherein Zn²⁺The content of (A) is 6.90 cation% or more.

7. The optical glass according to any one of claims 1 to 6, wherein Tc-Tg, which is a temperature difference between a crystallization peak temperature Tc and a glass transition temperature Tg, is 150 ℃ or more.

8. The optical glass according to any one of claims 1 to 6, wherein the haze value is 5% or less.

9. An optical element comprising the optical glass according to any one of claims 1 to 8.

10. An optical glass material comprising the optical glass according to any one of claims 1 to 8.