CN111892298A

CN111892298A - Optical glass, optical preform and optical element

Info

Publication number: CN111892298A
Application number: CN202010933683.1A
Authority: CN
Inventors: 蔡冬雪
Original assignee: CDGM Glass Co Ltd
Current assignee: CDGM Glass Co Ltd
Priority date: 2020-09-08
Filing date: 2020-09-08
Publication date: 2020-11-06

Abstract

The invention provides an optical glass, which comprises the following components in percentage by mole: p⁵⁺：19‑36％；Al³⁺：20‑35％；Ba²⁺：25‑40％；Sr²⁺: 5-20% of Al, wherein³⁺/P⁵⁺0.65-1.5; the anion containing F^‑And O^2‑Wherein F is^‑Content and F^‑And O^2‑The ratio F of the total content of^‑/(F^‑+O^2‑) Is 0.4-0.7. By reasonably adjusting the proportion of the components, the optical glass has expected refractive index and Abbe number, excellent anti-crystallization performance and chemical stability, and meets the development requirements of the modern photoelectric field.

Description

Optical glass, optical preform and optical element

Technical Field

The invention relates to an optical glass, in particular to an optical glass with a refractive index of 1.51-1.58 and an Abbe number of 70-80, and an optical preform and an optical element made of the optical glass.

Background

In an optical system such as a camera, in order to eliminate chromatic aberration of a lens, a design of "achromatizing" by combining glasses having different abbe numbers is generally adopted, and therefore, optical glasses having different refractive indexes and abbe numbers need to be combined to form a reasonable optical system. The fluorophosphate optical glass is used as a novel glass material with wider application, has the characteristic of low dispersion, can eliminate the special dispersion of a secondary spectrum in an optical system, improves the resolution ratio, obviously improves the imaging quality of the optical system, has lower softening temperature, and can be directly and precisely molded into a high-grade aspheric lens. However, the existing fluorophosphate optical glass with the refractive index of 1.51-1.58 and the Abbe number of 70-80 is generally poor in devitrification resistance, is easy to devitrify in the production and precision die pressing processes, and reduces the yield of the glass.

In recent years, optical glass is widely used in the fields of vehicle-mounted and monitoring security, and the like, and the optical glass used in the fields of vehicle-mounted and security is exposed outdoors for a long time, so that the requirement for chemical stability of the optical glass is high. Therefore, the demand of fluorophosphate optical glass having excellent chemical stability and devitrification resistance in the field of photoelectric materials is more and more urgent.

Disclosure of Invention

The invention aims to provide optical glass with excellent anti-crystallization performance and chemical stability.

The technical scheme adopted by the invention for solving the technical problem is as follows:

optical glass, the composition of which is expressed in mole percent, the cations comprising: p⁵⁺：19-36％；Al³⁺：20-35％；Ba² ⁺：25-40％；Sr²⁺: 5-20% of Al, wherein³⁺/P⁵⁺0.65-1.5;

the anion containing F^-And O^2-Wherein F is^-Content and F^-And O^2-The ratio F of the total content of^-/(F^-+O^2-) Is 0.4-0.7.

Further, the optical glass comprises the following components in mol percent, and the cation further comprises: ca²⁺: 0 to 10 percent; and/or Mg²⁺: 0 to 10 percent; and/or Si⁴⁺: 0 to 10 percent; and/or B³⁺: 0 to 10 percent; and/or Na⁺: 0 to 10 percent; and/or Li⁺: 0 to 10 percent; and/or K⁺: 0 to 10 percent; and/or Zn²⁺: 0 to 10 percent; and/or Nb⁵⁺: 0 to 10 percent; and/or Ti⁴⁺: 0 to 10 percent; and/or Zr⁴⁺: 0 to 10 percent; and/or W⁶⁺：0-10％。

Optical glass having a composition expressed in mole percent with cations represented by P⁵⁺：19-36％；Al³⁺：20-35％；Ba²⁺：25-40％；Sr²⁺：5-20％；Ca²⁺：0-10％；Mg²⁺：0-10％；Si⁴⁺：0-10％；B³⁺：0-10％；Na⁺：0-10％；Li⁺：0-10％；K⁺：0-10％；Zn²⁺：0-10％；Nb⁵⁺：0-10％；Ti⁴⁺：0-10％；Zr⁴⁺：0-10％；W⁶⁺：0-10％；Sb³ ⁺：0-1％；Sn⁴⁺：0-1％；Ce⁴⁺: 0-1% of a composition wherein Al³⁺/P⁵⁺0.65-1.5;

the anion is formed by F^-、O^2-And 0-1% Cl^-Composition of, wherein, F^-Content and F^-And O^2-The ratio F of the total content of^-/(F^-+O^2-) Is 0.4-0.7.

Further, the optical glass has the components expressed by mole percent, and each component satisfies more than one of the following 5 conditions:

1)Sr²⁺the content is more than Mg²⁺Content (c);

2)Ba²⁺/R²⁺is more than 0.5;

3)Mg²⁺/Ca²⁺is less than 0.9;

4)Sr²⁺/Ba²⁺0.15-0.6;

5)Al³⁺/P⁵⁺is in the range of 0.7 to 1.4,

wherein R is²⁺Is Ba²⁺、Sr²⁺、Ca²⁺、Mg²⁺The total content of (a).

Further, the optical glass comprises the following components in mol percentage: p⁵⁺: 24 to 35 percent; and/or Al³⁺: 25 to 34 percent; and/or Ba²⁺: 26 to 37 percent; and/or Sr²⁺: 5 to 18 percent; and/or Ca²⁺: 0 to 8 percent; and/or Mg²⁺: 0 to 8 percent; and/or Si⁴⁺: 0 to 5 percent; and/or B³⁺: 0 to 5 percent; and/or Na⁺: 0 to 5 percent; and/or Li⁺: 0 to 5 percent; and/or K⁺: 0 to 5 percent; and/or Zn²⁺: 0 to 5 percent; and/or Nb⁵⁺: 0 to 5 percent; and/or Ti⁴⁺: 0 to 5 percent; and/or Zr⁴⁺: 0 to 5 percent; and/or W⁶⁺：0-5％。

Further, the optical glass has the components expressed by mole percent, and each component satisfies more than one of the following 4 cases:

1)Ba²⁺/R²⁺0.6-0.95;

2)Mg²⁺/Ca²⁺0.75 or less;

3)Sr²⁺/Ba²⁺0.15-0.5;

4)Al³⁺/P⁵⁺is in the range of 0.8 to 1.3,

Further, the optical glass has a composition expressed by mole percent, P⁵⁺: 27 to 35 percent; and/or Al³⁺: 27 to 34 percent; and/or Ba²⁺: 28 to 35 percent; and/or Sr²⁺: 6-15%, preferably Sr²⁺: 6 to 12 percent; and/or Ca²⁺: 0.5 to 5 percent; and/or Mg²⁺: 0-5%, preferably Mg²⁺: 0 to 3 percent; and/or Si⁴⁺: 0 to 3 percent; and/or B³⁺: 0 to 3 percent; and/or Na⁺: 0 to 3 percent; and/or Li⁺: 0 to 3 percent; and/or K⁺: 0 to 3 percent; and/or Zn²⁺: 0 to 3 percent; and/or Nb⁵⁺: 0 to 3 percent; and/or Ti⁴⁺: 0 to 3 percent; and/or Zr⁴ ⁺: 0 to 3 percent; and/or W⁶⁺：0-3％。

1)Ba²⁺/R²⁺0.65-0.9;

2)Mg²⁺/Ca²⁺is 0.6 or less;

3)Sr²⁺/Ba²⁺0.2-0.4;

4)Al³⁺/P⁵⁺is in the range of 0.9 to 1.2,

Furthermore, the optical glass,the components are expressed by mole percent, wherein: ba²⁺/R²⁺0.7-0.85, and/or Mg²⁺/Ca²⁺Is 0.4 or less, wherein R²⁺Is Ba²⁺、Sr²⁺、Ca²⁺、Mg²⁺The total content of (a).

Further, the optical glass comprises the following components in mol percentage: f^-: 40-70%, preferably F^-: 45-70%, more preferably F^-: 45-60 percent; and/or O^2-: 30-60%, preferably O^2-: 30-55%, more preferably O^2-：40-55％。

Further, the optical glass comprises the following components in mol percentage: f^-/(F^-+O^2-) Is 0.45-0.7, preferably F^-/(F^-+O^2-) Is 0.45-0.6.

Further, the optical glass comprises the following components in mol percent, and the cation further comprises: sb³⁺: 0 to 1 percent; and/or Sn⁴⁺: 0 to 1 percent; and/or Ce⁴⁺: 0 to 1 percent; the anion also contains: cl^-: 0 to 1 percent; and/or Br^-: 0 to 1 percent; and/or I^-: 0-1%, preferably the anion also contains: cl^-: 0 to 0.5 percent; and/or Br^-: 0 to 0.5 percent; and/or I^-: 0-0.5%, more preferably the anion further comprises: cl^-: 0 to 0.2 percent; and/or Br^-: 0 to 0.2 percent; and/or I^-：0-0.2％。

Further, the optical glass does not contain Li in the components⁺(ii) a And/or do not contain B³⁺(ii) a And/or does not contain Zn²⁺。

Further, the refractive index n of the optical glass_dFrom 1.51 to 1.58, preferably from 1.51 to 1.56, more preferably from 1.515 to 1.54; abbe number v_dFrom 70 to 80, preferably from 71 to 78, more preferably from 73 to 77.

Further, the transition temperature T of the optical glass_g530 ℃ or lower, preferably 520 ℃ or lower, more preferably 510 ℃ or lower; and/or the density rho of the optical glass is 4.40g/cm³The following are preferredIs 4.30g/cm³Hereinafter, more preferably 4.20g/cm³The following; and/or stability against water action D_WIs 2 or more, preferably 1; and/or stability against acid action D_AIs 2 or more, preferably 1; and/or the anti-devitrification performance is more than B level, preferably A level.

And the optical prefabricated member is made of the optical glass.

And the optical element is made of the optical glass or the optical prefabricated member.

An optical device comprising the above optical glass and/or comprising the above optical element.

The invention has the beneficial effects that: by reasonably adjusting the proportion of the components, the optical glass has expected refractive index and Abbe number, excellent anti-crystallization performance and chemical stability, and meets the development requirements of the modern photoelectric field.

Detailed Description

The optical glass of the present invention is obtained by the following steps, which are not limited to the above-described embodiments, and can be appropriately modified within the scope of the object of the present invention. Although the description of the overlapping portions may be omitted as appropriate, the gist of the present invention is not limited thereto, and the optical glass of the present invention may be simply referred to as glass in the following description.

I, optical glass

In the present invention, the content of each constituent component (component) of the optical glass is not particularly specified, and the cationic component content is expressed in terms of the percentage (mol%) of the cation to the total mole of all the cationic components, and the anionic component content is expressed in terms of the percentage (mol%) of the anion to the total mole of all the anionic components.

Unless otherwise indicated herein, the numerical ranges set forth herein include upper and lower values, and the terms "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values listed in the defined range. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means A alone, B alone, or both A and B.

The ion valence of each component described in the present invention is a representative value used for convenience, and is not different from other ion valence. The ion valence of each component present in the optical glass may be out of the representative value. For example, P is usually present in the glass in a state where the ion valence is 5, and hence "P" is used in the present specification⁵⁺"as a representative, but there is a possibility that the ion valence is in other states, and this is also within the scope of the present invention.

[ regarding the cationic component ]

P⁵⁺Is a glass network former component, and when the content thereof is less than 19%, the stability of the glass is lowered. On the other hand, by controlling P⁵⁺When the content is 36% or less, devitrification of the glass can be suppressed, and lowering of the abbe number of the glass can be suppressed, and a stable glass having low dispersion can be easily obtained. Thus, P⁵⁺The content is limited to 19 to 36%, preferably 24 to 35%, more preferably 27 to 35%.

Al³⁺The thermal stability of the glass can be improved, the processability and the chemical stability of the glass can be effectively improved, and the average linear expansion coefficient of the glass can be reduced. When the content thereof is less than 20%, a stable glass skeleton cannot be formed and the above-mentioned effects are obtained; when the content is higher than 35%, the transition temperature and the liquidus temperature of the glass are increased, so that melting becomes difficult, and simultaneously, the temperature is increased during forming, so that volatilization of the glass is aggravated, and the glass stripes are deteriorated; on the other hand, too high a transition temperature makes press molding difficult. Thus, Al³⁺The content is 20 to 35%, preferably 25 to 34%, more preferably 27 to 34%.

In some embodiments, when Al³⁺And P⁵⁺Ratio of (A) to (B) Al³⁺/P⁵⁺When the glass content is more than 1.5, the devitrification resistance of the glass is deteriorated; when Al is present³⁺And P⁵⁺Ratio of (A) to (B) Al³⁺/P⁵⁺When the amount is less than 0.65, the chemical stability of the glass is lowered. Thus, Al³⁺/P⁵⁺Is in the range of 0.65 to 1.5,preferably 0.7 to 1.4, more preferably 0.8 to 1.3, and further preferably 0.9 to 1.2.

Mg²⁺The degree of abrasion of the glass can be increased to some extent, but if the content exceeds 10%, devitrification resistance and hardness of the glass are lowered, so that Mg²⁺The content range of (b) is limited to 0 to 10%, preferably 0 to 8%, more preferably 0 to 5%, and further preferably 0 to 3%.

Ca²⁺The optical glass of the present invention has the effect of improving devitrification resistance of the glass, suppressing a decrease in refractive index, and reducing the degree of abrasion of the glass, but when the content thereof exceeds 10%, devitrification resistance of the glass is rather deteriorated. Therefore, Ca in the optical glass of the present invention²⁺The content range of (b) is defined as 0 to 10%, preferably 0 to 8%, more preferably 0.5 to 5%.

The inventors have discovered, through research, that in some embodiments, when Mg is present²⁺Content and Ca²⁺Ratio of contents Mg²⁺/Ca²⁺When the content is 0.9 or less, the water resistance stability and weather resistance of the glass can be improved, the devitrification resistance of the glass can be optimized, and Mg is preferable²⁺/Ca²⁺Is 0.75 or less, more preferably Mg²⁺/Ca²⁺Is 0.6 or less, and Mg is more preferable²⁺/Ca²⁺Is 0.4 or less.

Sr²⁺The linear expansion coefficient of the glass can be reduced and the refractive index and density of the glass can be effectively adjusted, but if the content is too high, the refractive index and dispersion of the glass become large, it is difficult to achieve desired optical constants, and the chemical stability of the glass is also reduced. Therefore, in the present invention, Sr²⁺The content range of (B) is limited to 5 to 20%, preferably 5 to 18%, more preferably 6 to 15%, and still more preferably 6 to 12%. In some embodiments, to obtain excellent anti-devitrification properties, optical transmittance and linear expansion coefficient, Sr is preferred²⁺The content is more than Mg²⁺And (4) content.

The optical glass of the present invention contains more than 25% of Ba²⁺As an essential component, the devitrification resistance and the chemical stability of the glass can be improved, and meanwhile, the linear expansion coefficient of the glass can be reduced, and low dispersibility and higher hardness are maintained; when the content exceedsAt 40%, the density of the glass increases, making it difficult to satisfy the requirement of weight reduction, and the thermal stability of the glass decreases. Therefore, Ba is contained in the optical glass of the present invention²⁺The content range of (B) is limited to 25 to 40%, preferably 26 to 37%, and more preferably 28 to 35%.

In some embodiments, by preferring Sr²⁺Content and Ba²⁺Content ratio Sr²⁺/Ba²⁺0.15 to 0.6, which can make the glass of the invention have excellent temperature coefficient of refractive index and anti-devitrification performance, and simultaneously can reduce the linear expansion coefficient, the transition temperature and the density of the glass, preferably Sr²⁺/Ba²⁺0.15 to 0.5, more preferably Sr²⁺/Ba²⁺Is 0.2-0.4.

In the glass of the present invention, Ba is controlled²⁺And Ba²⁺、Sr²⁺、Ca²⁺And Mg²⁺Total content R of²⁺Ratio of Ba²⁺/R²⁺Above 0.5, can improve the temperature coefficient of refractive index of the glass, improve the devitrification resistance of the glass, increase the chemical stability and hardness of the glass, preferably Ba²⁺/R²⁺Is 0.6 to 0.95, more preferably Ba²⁺/R²⁺Is 0.65 to 0.9, more preferably Ba²⁺/R²⁺Is 0.7-0.85.

Li⁺The transition temperature of the glass can be effectively reduced in the glass. However, optical glass is generally melted using a platinum or platinum alloy vessel, and Li in the glass component is melted at a high temperature⁺The platinum or platinum alloy vessel is easy to corrode, and the finished glass generates more platinum-containing foreign matters, thereby causing the quality of the glass to be reduced. On the other hand, when such glasses are used in precision press molding, there is a risk that the surface of the glass member is easily blurred because the mold is generally coated with a release agent containing a carbon element, and Li in the glass component⁺Easily react with carbon element in the release agent to generate a rough opaque film layer on the surface of the glass element. Thus, Li in the present invention⁺The content of (B) is limited to 0 to 10%, preferably 0 to 5%, more preferably 0 to 3%, and further preferably Li is not contained⁺。

Na⁺Can improve the meltability of the glass and reduce the melting point of the glassYield point and liquidus temperature, however, when the content exceeds 10%, deterioration of devitrification resistance of the glass is accelerated, and at the same time, the time for the glass to change from a liquid state to a solid state is prolonged during cooling molding, providing conditions for devitrification, so that the content is controlled to 10% or less, preferably 0 to 5%, more preferably 0 to 3%.

K⁺As optional components in the present invention, it is possible to maintain the devitrification resistance and lower the transition temperature at the time of glass forming, but when it exceeds 10%, it results in deterioration of the water resistance of the glass, so that K is⁺The content is limited to 10% or less, preferably 5% or less, and more preferably 3% or less.

Si⁴⁺It is possible to improve the devitrification resistance and refractive index of the glass, to reduce the degree of abrasion of the glass and to improve the processability, and when the content exceeds 10%, the melting property of the glass is lowered, so that Si in the optical glass of the present invention⁴⁺The content is 0 to 10%, preferably 0 to 5%, more preferably 0 to 3%.

B³⁺The devitrification resistance of the glass can be improved, and the density of the glass can be reduced, but when the glass is added into the optical glass containing F, the glass is melted and is subjected to relatively strong volatilization, so that the optical constant of the glass is unstable, and the degree of striae is poor. Thus B³⁺The content is limited to 10% or less, preferably 5% or less, more preferably 3% or less, and further preferably no B is contained³⁺。

Nb⁵⁺Belongs to a high-refraction high-dispersion component, can improve the refractive index in the glass and adjust the Abbe number of the glass. In the glass of the system of the invention, if the content is more than 10 percent, the refractive index and Abbe number of the glass can not meet the design requirements, and the devitrification resistance of the glass is reduced sharply. Thus, Nb⁵⁺The content of (B) is 0 to 10%, preferably 0 to 5%, more preferably 0 to 3%.

Zn²⁺Has the effects of improving the thermal stability of the glass and lowering the transition temperature of the glass, and when the content thereof exceeds 10%, the dispersion of the glass increases, it becomes difficult to obtain a desired optical constant, and the devitrification resistance of the glass decreases. Thus, Zn²⁺The content is limited to 10% or less, preferably 5% or less, more preferably 3% or less, and further preferably no Zn is contained²⁺。

Zr⁴⁺The addition of an appropriate amount of (B) can suppress the formation of striae due to volatilization in the glass, and when the content exceeds 10%, the optical constant is difficult to control, so that the content is limited to 10% or less, preferably 5% or less, and more preferably 3% or less.

Ti⁴⁺The devitrification resistance of the glass can be improved, and if the content thereof is more than 10%, the refractive index of the glass is increased and the transmittance is decreased. Thus, Ti⁴⁺The content of (B) is limited to 0 to 10%, preferably 0 to 5%, more preferably 0 to 3%.

W⁶⁺Is a component for increasing the refractive index of the glass, is an optional component in the glass of the invention, in particular for increasing the W content of the glass⁶⁺The content of (b) is 10% or less, and the coloring of the glass can be reduced while suppressing the lowering of the Abbe number of the glass, and the content is preferably 0 to 5%, more preferably 0 to 3%.

In some embodiments, Sb may be added³⁺、Sn⁴⁺、Ce⁴⁺And the like as a fining agent to improve the fining effect of the glass, specifically, they may be present in the glass in a content of 1% or less, and preferably in a content of 0.5% or less, respectively.

[ regarding the anionic component ]

The anion in the optical glass of the present invention is mainly F^-And O^2-In order to obtain the desired properties of the optical glass of the present invention, F in the optical glass of the present invention^-Content and F^-And O^2-The ratio F of the total content of^-/(F^-+O^2-) Is 0.4-0.7, preferably F^-/(F^-+O^2-) Is 0.45 to 0.7, more preferably F^-/(F^-+O^2-) Is 0.45-0.6.

F^-Has great effect on reducing the temperature coefficient of the refractive index and the transition temperature, and is an important component for improving the Abbe number and the abnormal dispersibility. If the content is too high, the stability of the glass is impaired and the coefficient of thermal expansion is increased, especially during melting, F^-The volatilization of the glass not only pollutes the environment, but also causes the internal composition of the glass to be uneven, thereby causing defects such as data abnormity, stripes and the like. When the content is less than 40%, the desired Abbe number and abnormality cannot be obtainedDispersibility; if the content is more than 70%, Abbe number of the glass becomes excessively large and volatilization sharply increases at the time of melting and use for precision press-molding, so that F^-The content is limited to 40 to 70%, preferably 45 to 70%, more preferably 45 to 60%.

The optical glass of the present invention contains O^2-Especially by containing more than 30% of O^2-The devitrification of the glass and the increase in the abrasion degree can be suppressed. Thus O^2-The content of (b) is limited to 30% or more, preferably 40% or more. On the other hand, by mixing O^2-The content of (B) is limited to 60% or less, and the effect of other anionic components can be more effectively obtained while ensuring the stability of the glass, so that O in the present invention^2-The content is 60% or less, preferably 55% or less.

In some embodiments of the present invention, 0-1% Cl may be added separately to improve the fining effect of the glass^-、Br^-And I^-The content of (b) is preferably 0.5% or less, and more preferably 0.2% or less.

[ regarding components that should not be contained ]

Other components not mentioned above can be added as necessary within the range not impairing the characteristics of the glass of the present invention. However, it is preferable that the transition metal components such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo are not substantially contained in the optical glass which transmits a wavelength in the visible light region because the glass is colored and absorbs a specific wavelength in the visible light region to weaken the effect of improving the visible light transmittance of the present invention even when the transition metal components are contained in a small amount individually or in combination.

In recent years, cations of Pb, Th, Cd, Tl, Os, Be, and Se tend to Be used as harmful chemical substances under control, and environmental measures are required not only in the glass production process but also in the processing process and disposal after commercialization. Therefore, when importance is attached to the environmental influence, it is preferable that these components are not substantially contained except for inevitable mixing. Thus, the optical glass contains virtually no substances contaminating the environment. Therefore, the optical glass of the present invention can be manufactured, processed, and discarded without taking special measures for environmental measures.

"0%" or "0%" as used herein means that the component or the like is not intentionally added as a raw material to the optical glass of the present invention; however, it is within the scope of the present invention that certain impurities or components which are not intentionally added may be present as raw materials and/or equipment for producing the optical glass and may be contained in the final optical glass in small or trace amounts.

The properties of the optical glass of the present invention will be described below.

[ refractive index and Abbe number ]

Refractive index (n) of the optical glass of the present invention_d) And Abbe number (v)_d) The test was carried out according to the method specified in GB/T7962.1-2010.

Refractive index (n) of the optical glass of the present invention_d) From 1.51 to 1.58, preferably from 1.51 to 1.56, more preferably from 1.515 to 1.54; abbe number (v) of the optical glass of the present invention_d) From 70 to 80, preferably from 71 to 78, more preferably from 73 to 77.

[ transition temperature ]

Transition temperature (T) of optical glass_g) The measurement was carried out according to the method specified in GB/T7962.16-2010.

Transition temperature (T) of the glasses according to the invention_g) 530 ℃ or lower, preferably 520 ℃ or lower, and more preferably 510 ℃ or lower.

[ Density ]

The density (. rho.) of the optical glass was measured by the method specified in GB/T7962.20-2010.

The density (. rho.) of the glass of the present invention is 4.40g/cm³Hereinafter, it is preferably 4.30g/cm³Hereinafter, more preferably 4.20g/cm³The following.

[ stability against Water action ]

Stability to Water action by glass powder method (D)_W) Measured using the GB/T17129 test standard.

Stability to Water action of the optical glass of the invention (D)_W) Is 2 or more, preferably 1.

[ stability against acid action ]

Stability to acid action by glass powder method (D)_A) Measured using the GB/T17129 test standard.

Stability of acid resistance of the optical glass of the present invention (D)_A) Is 2 or more, preferably 1.

[ anti-devitrification Property ]

The crystallization performance of the glass is detected by adopting the following method:

processing the test sample to 20 × 10mm specification, polishing both sides, placing the sample at temperature T_gAnd (3) keeping the temperature in a crystallization furnace at 200 ℃ for 30 minutes, taking out and cooling, polishing the two large surfaces, and judging the crystallization performance of the glass according to the following table 1, wherein the A grade is the best, and the E grade is the worst.

Table 1: classification and judgment criteria for devitrification

Numbering	Rank of	Standard of merit
			1	A	Devitrified particles without macroscopic view
2	B	The crystallized particles are visible to the naked eye, and are small in number and dispersed
			3	C	Larger dispersed or denser, smaller devitrified particles are visible to the naked eye
4	D	The crystallized grains are larger and dense
			5	E	Complete devitrification and devitrification of glass

The optical glass of the present invention has devitrification resistance of class B or higher, preferably class A.

II, optical preform and optical element

Next, the optical preform and the optical element of the present invention are described.

The optical preform and the optical element of the present invention are each formed of the above-described optical glass of the present invention. The optical preform of the present invention has low dispersion characteristics; the optical element of the present invention has low dispersion characteristics, and can provide optical elements such as various lenses and prisms having high optical values at low cost.

From the optical glass to be produced, an optical preform can be produced by press molding means such as reheat press molding and precision press molding. That is, an optical glass molding material for press molding can be produced from an optical glass, and an optical preform can be produced by subjecting the optical glass molding material to reheat press molding and then to polishing. The means for producing the optical preform is not limited to the above.

The optical preforms so produced are useful in a variety of optical elements and optical designs. In particular, it is preferable to manufacture optical elements such as lenses, prisms, and mirrors from the optical glass of the present invention by means of precision press molding or the like. Accordingly, when used in an optical device that transmits visible light in an optical element such as a camera or a projector, high-definition and high-precision imaging characteristics can be achieved, and the weight of an optical system in the optical device can be reduced.

Examples of the lens include various lenses such as a concave meniscus lens, a convex meniscus lens, a double convex lens, a double concave lens, a plano-convex lens, and a plano-concave lens, each of which has a spherical or aspherical lens surface. The lens can correct chromatic aberration by combining with a lens made of high-refractivity high-dispersion glass, and is suitable as a lens for chromatic aberration correction. Further, the lens is also effective for the compactness of an optical system.

III, optical instrument

The optical glass and/or the optical element formed by the optical glass can be used for manufacturing optical instruments such as photographic equipment, camera equipment, display equipment, monitoring equipment and the like.

[ method for producing optical glass ]

The melting and forming method of the optical glass of the present invention can employ techniques known to those skilled in the art. Namely: the method comprises the steps of mixing glass raw materials (fluoride, carbonate, nitrate, sulfate, phosphate, metaphosphate, oxide, boric acid, hydroxide and the like) according to a conventional method, uniformly mixing, putting into a smelting device (such as a platinum crucible, a quartz crucible and the like), then carrying out proper stirring, clarification and homogenization at 900-1200 ℃ to obtain homogeneous molten glass without bubbles and undissolved substances, cooling to below 900 ℃, casting the molten glass in a mold, and annealing. Those skilled in the art can appropriately select the raw materials, the process method and the process parameters according to the actual needs.

Examples

In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided.

[ optical glass examples ]

In this example, optical glasses having optical glass compositions shown in tables 2 to 3 were obtained by the above-mentioned optical glass production method. In addition, the characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in tables 2 to 3.

Table 2.

Table 3.

[ optical preform examples ]

The optical glasses obtained in examples 1 to 10 in table 2 were cut into a predetermined size, and then a release agent was uniformly applied to the surface of the optical glass, followed by heating, softening, and press-molding to prepare preforms of various lenses and prisms such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, and a plano-concave lens.

[ optical element examples ]

The preforms obtained in the above examples of glass preforms were annealed to reduce the deformation in the glass and to fine-tune the optical properties such as refractive index to desired values.

Next, each preform is ground and polished to produce various lenses such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, and a plano-concave lens, and prisms. The surface of the optical element may be coated with an antireflection film.

[ optical instrument example ]

The optical element obtained by the above-described optical element embodiment is optically designed to form an optical component or an optical assembly by using one or more optical elements, and can be used, for example, for imaging devices, sensors, microscopes, medical technologies, digital projection, communications, optical communication technologies/information transmission, optics/lighting in the automotive field, photolithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, or for camera devices and apparatuses in the field of vehicle-mounted, surveillance and security.

Claims

1. Optical glass, characterized in that its composition, expressed in mole percentages, has a cation comprising: p⁵⁺：19-36％；Al³⁺：20-35％；Ba²⁺：25-40％；Sr²⁺: 5-20% of Al, wherein³⁺/P⁵⁺0.65-1.5;

2. An optical glass according to claim 1, characterised in that its composition, expressed in mole percent, the cations also contain: ca²⁺: 0 to 10 percent; and/or Mg²⁺: 0 to 10 percent; and/or Si⁴⁺: 0 to 10 percent; and/or B³⁺: 0 to 10 percent; and/or Na⁺: 0 to 10 percent; and/or Li⁺: 0 to 10 percent; and/or K⁺: 0 to 10 percent; and/or Zn²⁺: 0 to 10 percent; and/or Nb⁵⁺: 0 to 10 percent; and/or Ti⁴⁺: 0 to 10 percent; and/or Zr⁴⁺: 0 to 10 percent; and/or W⁶⁺：0-10％。

3. Optical glass, characterised in that its composition is expressed in mole percentage and the cations are represented by P⁵⁺：19-36％；Al³⁺：20-35％；Ba²⁺：25-40％；Sr²⁺：5-20％；Ca²⁺：0-10％；Mg²⁺：0-10％；Si⁴⁺：0-10％；B³⁺：0-10％；Na⁺：0-10％；Li⁺：0-10％；K⁺：0-10％；Zn²⁺：0-10％；Nb⁵⁺：0-10％；Ti⁴⁺：0-10％；Zr⁴⁺：0-10％；W⁶⁺：0-10％；Sb³⁺：0-1％；Sn⁴⁺：0-1％；Ce⁴⁺: 0-1% of a composition wherein Al³⁺/P⁵⁺0.65-1.5;

4. An optical glass according to any of claims 1-3, characterised in that its components, expressed in mole percentage, satisfy one or more of the following 5 cases:

1)Sr²⁺the content is more than Mg²⁺Content (c);

2)Ba²⁺/R²⁺is more than 0.5;

3)Mg²⁺/Ca²⁺is less than 0.9;

4)Sr²⁺/Ba²⁺0.15-0.6;

5)Al³⁺/P⁵⁺is in the range of 0.7 to 1.4,

5. An optical glass according to any one of claims 1 to 3, characterised in that its composition is expressed in mole percentages in which: p⁵⁺: 24 to 35 percent; and/or Al³⁺: 25 to 34 percent; and/or Ba²⁺: 26 to 37 percent; and/or Sr²⁺: 5 to 18 percent; and/or Ca²⁺: 0 to 8 percent; and/or Mg²⁺: 0 to 8 percent; and/or Si⁴⁺: 0 to 5 percent; and/or B³⁺: 0 to 5 percent; and/or Na⁺: 0 to 5 percent; and/or Li⁺: 0 to 5 percent; and/or K⁺: 0 to 5 percent; and/or Zn²⁺: 0 to 5 percent; and/or Nb⁵⁺: 0 to 5 percent; and/or Ti⁴⁺: 0 to 5 percent; and/or Zr⁴⁺: 0 to 5 percent; and/or W⁶⁺：0-5％。

6. An optical glass according to any of claims 1 to 3, characterised in that its components, expressed in mole percentage, satisfy more than one of the following 4 cases:

1)Ba²⁺/R²⁺0.6-0.95;

2)Mg²⁺/Ca²⁺0.75 or less;

3)Sr²⁺/Ba²⁺0.15-0.5;

4)Al³⁺/P⁵⁺is in the range of 0.8 to 1.3,

7. An optical glass according to any one of claims 1 to 3, characterised in that its composition, expressed in mole percentage, is P⁵⁺: 27 to 35 percent; and/or Al³⁺: 27 to 34 percent; and/or Ba²⁺: 28 to 35 percent; and/or Sr²⁺: 6-15%, preferably Sr²⁺: 6 to 12 percent; and/or Ca²⁺: 0.5 to 5 percent; and/or Mg²⁺: 0-5%, preferably Mg²⁺: 0 to 3 percent; and/or Si⁴⁺: 0 to 3 percent; and/or B³ ⁺: 0 to 3 percent; and/or Na⁺: 0 to 3 percent; and/or Li⁺: 0 to 3 percent; and/or K⁺: 0 to 3 percent; and/or Zn²⁺: 0 to 3 percent; and/or Nb⁵⁺: 0 to 3 percent; and/or Ti⁴⁺: 0 to 3 percent; and/or Zr⁴⁺: 0 to 3 percent; and/or W⁶⁺：0-3％。

8. An optical glass according to any of claims 1 to 3, characterised in that its components, expressed in mole percentage, satisfy more than one of the following 4 cases:

1)Ba²⁺/R²⁺0.65-0.9;

2)Mg²⁺/Ca²⁺is 0.6 or less;

3)Sr²⁺/Ba²⁺0.2-0.4;

4)Al³⁺/P⁵⁺is in the range of 0.9 to 1.2,

9. An optical glass according to any one of claims 1 to 3, characterised in that its composition is expressed in mole percentages in which: ba²⁺/R²⁺0.7-0.85, and/or Mg²⁺/Ca²⁺Is 0.4 or less, wherein R²⁺Is Ba²⁺、Sr²⁺、Ca²⁺、Mg²⁺The total content of (a).

10. An optical glass according to any one of claims 1 to 3, characterised in that its composition is expressed in mole percentages in which: f^-: 40-70%, preferably F^-: 45-70%, more preferably F^-: 45-60 percent; and/or O^2-: 30-60%, preferably O^2-: 30-55%, more preferably O^2-：40-55％。

11. An optical glass according to any one of claims 1 to 3, characterised in that its composition is expressed in mole percentages in which: f^-/(F^-+O^2-) Is 0.45-0.7, preferably F^-/(F^-+O^2-) Is 0.45-0.6.

12. An optical glass according to any one of claims 1 or 2, characterised in that its composition, expressed in mole percentage, cations further comprise: sb³⁺: 0 to 1 percent; and/or Sn⁴⁺: 0 to 1 percent; and/or Ce⁴⁺: 0 to 1 percent; the anion also contains: cl^-: 0 to 1 percent; and/or Br^-: 0 to 1 percent; and/or I^-: 0-1%, preferably the anion also contains: cl^-: 0 to 0.5 percent; and/or Br^-: 0 to 0.5 percent; and/or I^-: 0-0.5%, more preferably the anion further comprises: cl^-: 0 to 0.2 percent; and/or Br^-: 0 to 0.2 percent; and/or I^-：0-0.2％。

13. An optical glass according to any of claims 1 to 3, characterised in that its composition does not contain Li⁺(ii) a And/or do not contain B³⁺(ii) a And/or does not contain Zn²⁺。

14. An optical glass according to any of claims 1 to 3, characterised in that the refractive index n of the optical glass is_dFrom 1.51 to 1.58, preferably from 1.51 to 1.56, more preferably from 1.515 to 1.54; abbe number v_dFrom 70 to 80, preferably from 71 to 78, more preferably from 73 to 77.

15. An optical glass according to any of claims 1 to 3, characterised in that the transition temperature T of the optical glass_g530 ℃ or lower, preferably 520 ℃ or lower, more preferably 510 ℃ or lower; and/or the density rho of the optical glass is 4.40g/cm³Hereinafter, it is preferably 4.30g/cm³Hereinafter, more preferably 4.20g/cm³The following; and/or stability against water action D_WIs 2 or more, preferably 1; and/or stability against acid action D_AIs 2 or more, preferably 1; and/or the anti-devitrification performance is more than B level, preferably A level.

16. Optical preform, characterized in that it is made of an optical glass according to any one of claims 1 to 15.

17. Optical element, characterized in that it is made of an optical glass according to any one of claims 1 to 15 or an optical preform according to claim 16.

18. An optical instrument comprising the optical glass according to any one of claims 1 to 15 and/or comprising the optical element according to claim 17.