Optical glass, optical element and optical instrument

Abstract

The invention provides optical glass which has the refractive index of 1.46-1.52, the Abbe number of 81-89, excellent large-caliber forming performance and excellent thermal stability for large-caliber profiling. The optical glass comprises the following cation components in mole percentage: 7-27% of P < 5 + >; 10%-45% of Al < 3 + >; 5-25% of Ba < 2 + >; 5-25% of Sr < 2 + >; the anion component contains 50 to 90 percent of F <-> and 5 to 30 percent of Ca < 2 + >; and 10%-50% of O2 <->. By reasonably designing the content of each component, the optical glass has excellent large-caliber forming performance and excellent thermal stability for large-caliber profiling while ensuring excellent optical performance.

Description

Technical Field

[0001] The invention relates to an optical glass, in particular to an optical glass with a refractive index of 1.46-1.52 and an Abbe number of 81-89. Background Art

[0002] Fluorophosphate optical glass is a new type of glass material with a wide range of applications. It has the characteristics of low dispersion and low refractive index. It can eliminate the special dispersion of the secondary spectrum in the optical system, improve the resolution, and significantly improve the imaging quality of the optical system. In the prior art, fluorophosphate optical glass with a refractive index of 1.46 to 1.52 and an Abbe number of 81 to 89 is mainly used in small-aperture optical systems. Therefore, researchers pay more attention to the molding and precision molding performance of small-aperture fluorophosphate glass.

[0003] In recent years, with the rapid development of large-aperture precision optical equipment, the demand for large-aperture, high optical uniformity fluorophosphate glass has also increased. In the prior art, fluorophosphate glass with a refractive index of 1.46 to 1.52 and an Abbe number of 81 to 89 is prone to stripes inside the glass during large-aperture (thickness > 20 mm) molding, which leads to poor imaging quality of the optical element obtained. In addition, this type of glass has poor thermal stability and is difficult to achieve large-aperture precision molding. The above problems limit its use in large-aperture precision optical equipment. Summary of the invention

[0004] Based on the above reasons, the technical problem to be solved by the present invention is to provide an optical glass with a refractive index of 1.46-1.52, an Abbe number of 81-89, excellent large-diameter molding performance and excellent thermal stability for large-diameter pressing.

[0005] The technical solution adopted by the present invention to solve the technical problem is:

[0006] (1) Optical glass, the components of which are expressed in molar percentages, the cationic components containing: P 5+ :7~27%;Al 3+ :10~45%;Ba 2+ :5~25%; Sr 2+ :5~25%;Ca 2+ :5~30%,

[0007] The anionic component contains: F - :50~90%;O 2- :10~50%.

[0008] (2) The optical glass according to (1), wherein the components are expressed in molar percentages, and the cationic component further comprises: Mg 2+ :0~15%;and / or Y3+ : 0-10%; and / or La 3+ :0~10%;and / or Gd 3+ :0~10%;and / or R + :0~10%;and / or Sb 3+ :0~1%,the R + For Li + 、Na + , K + One or more of .

[0009] (3) The optical glass according to (1), wherein the components are expressed in molar percentages, and the anion component further comprises: Cl - :0~1%.

[0010] (4) Optical glass, the components of which are expressed in molar percentages, the cationic component is P 5+ :7~27%;Al 3+ :10~45%;Ba 2+ :5~25%; Sr 2+ :5~25%;Ca 2+ :5~30%;Mg 2+ :0~15%;Y 3+ :0~10%; La 3+ :0~10%;Gd 3+ :0~10%;R + :0~10%; Sb 3+ : 0~1% composition, the R + For Li + 、Na + , K + One or more of the anion component is F - :50~90%; 2- :10~50%;Cl - : 0~1% composition.

[0011] (5) The optical glass according to any one of (1) to (4), wherein the components thereof, expressed in molar percentage, satisfy one or more of the following five conditions:

[0012] 1)(Ba 2+ +Sr 2+ +Ca 2+ ) / Ba 2+ 2.0 to 4.6, preferably 2.5 to 4.1, more preferably 3.0 to 3.9;

[0013] 2)(45%-Al 3+ ) / (15%-Mg 2+ ) is 0.3 to 5.0, preferably (45%-Al3+ ) / (15%-Mg 2+ ) is 0.4 to 4.0, more preferably (45%-Al 3+ ) / (15%-Mg 2+ ) is 0.5 to 3.0, and more preferably (45%-Al 3+ ) / (15%-Mg 2+ ) is 0.6~2.0;

[0014] 3)(Al 3+ +Mg 2+ ) / Ba 2+ 1.5 to 3.5, preferably (Al 3+ +Mg 2+ ) / Ba 2+ 2.0 to 3.0, more preferably (Al 3+ +Mg 2+ ) / Ba 2+ 2.3~2.7;

[0015] 4)(45%-Al 3+ ) / (Gd 3+ +Y 3+ +La 3+ +Li + ) is 2.0 to 80.0, preferably (45%-Al 3+ ) / (Gd 3+ +Y 3+ +La 3+ +Li + ) is 6.0 to 50.0, more preferably (45%-Al 3+ ) / (Gd 3+ +Y 3+ +La 3+ +Li + ) is 8.0~35.0.

[0016] (6) The optical glass according to any one of (1) to (4), wherein the components are expressed in molar percentages, wherein: Mg 2+ / Al 3 + 0 to 0.5, preferably Mg 2+ / Al 3+ 0 to 0.3, more preferably Mg 2+ / Al 3+ 0 to 0.1; and / or (Al 3+ -Mg 2+ -Li + ) / P 5+ 0.5 to 2.5, preferably (Al 3+ -Mg 2+ -Li+ ) / P 5+ is 1.0 to 2.3, more preferably (Al 3+ -Mg 2+ -Li + ) / P 5+ is 1.3 to 2.1.

[0017] (7) The optical glass according to any one of (1) to (4), wherein the components are expressed in mole percentages, where: P 5+ : 11 to 24%, preferably P 5+ : 15 to 20%; and / or Al 3+ : 18 to 40%, preferably Al 3+ : 24 to 35%; and / or Ba 2+ : 9 to 21%, preferably Ba 2+ : 12 to 19%; and / or Sr 2+ : 8 to 21%, preferably Sr 2+ : 11 to 17%; and / or Ca 2+ : 10 to 25%, preferably Ca 2+ : 15 to 20%; and / or Mg 2+ : 0 to 10%, preferably Mg 2+ : 0 to 5%; and / or Y 3+ : 0 to 5%, preferably Y 3+ : 0 to 3%; and / or La 3+ : 0 to 5%, preferably La 3+ : 0 to 2%; and / or Gd 3+ : 0 to 5%, preferably Gd 3+ : 0 to 5%; and / or R + : 0 to 6%, preferably R + : 0 to 3%, more preferably does not contain R + ; and / or Sb 3+ : 0 to 0.5%, preferably Sb 3+ : 0 to 0.3%, where the R + is Li + 、Na + 、K + one or more of.

[0018] (8) The optical glass according to any one of (1) to (4), wherein the components are expressed in mole percentages, where: F - : 60 to 80%, preferably F - : 67 to 75%; and / or O 2- : 20 to 40%, preferably O 2- : 25 to 33%; and / or Cl - : 0 to 0.5%, preferably Cl -:0~0.3%.

[0019] (9) The optical glass according to any one of (1) to (4), wherein the refractive index n of the optical glass is d The refractive index n is preferably 1.46 to 1.52. d The refractive index n is preferably 1.47 to 1.51. d 1.48~1.50; Abbe number ν d 81 to 89, preferably Abbe number ν d 83 to 88, more preferably Abbe number ν d It is 84 to 87.

[0020] (10) The optical glass according to any one of (1) to (4), wherein λ 80 Less than or equal to 340nm, preferably λ 80 Less than or equal to 335nm, more preferably λ 80 Less than or equal to 330nm, more preferably λ 80 Less than or equal to 325nm, more preferably λ 80 less than or equal to 320nm; and / or λ5 is less than or equal to 265nm, preferably λ5 is less than or equal to 260nm, more preferably λ5 is less than or equal to 255nm, further preferably λ5 is less than or equal to 250nm, and further preferably λ5 is less than or equal to 245nm; and / or density ρ is 3.90g / cm 3 Below, the preferred density ρ is 3.82 g / cm 3 Below, the more preferred density ρ is 3.78 g / cm 3 Below, the density ρ is further preferably 3.74 g / cm 3 Below; and / or transition temperature T g The transition temperature T is preferably below 500°C. g The transition temperature is preferably 490°C or less. g is below 480°C; and / or the acid resistance stability RA is Class 3 or above, preferably the acid resistance stability RA is Class 2 or above; and / or the moisture resistance stability RC is Class 2 or above, preferably the moisture resistance stability RC is Class 1; and / or the stripe degree is Class C or above, preferably the stripe degree is Class B or above, and more preferably the stripe degree is Class A; and / or the anti-crystallization performance is Class D or above, preferably the anti-crystallization performance is Class C or above, more preferably the anti-crystallization performance is Class B, and further preferably the anti-crystallization performance is Class A.

[0021] (11) A glass preform made of the optical glass described in any one of (1) to (10).

[0022] (12) An optical element, made of the optical glass described in any one of (1) to (10), or made of the glass preform described in (11).

[0023] (13) An optical instrument comprising the optical glass described in any one of (1) to (10) and / or the optical element described in (12).

[0024] The beneficial effect of the present invention is that by reasonably designing the contents of the components, the optical glass of the present invention not only has excellent optical properties, but also has excellent large-diameter molding properties and excellent thermal stability for large-diameter pressing. DETAILED DESCRIPTION

[0025] The following will describe the embodiments of the optical glass of the present invention in detail, but the present invention is not limited to the following embodiments, and can be implemented by appropriate changes within the scope of the purpose of the present invention. In addition, although there are appropriate omissions of descriptions of the repeated descriptions, the gist of the invention will not be limited thereby, and in the following content, the optical glass of the present invention is sometimes referred to as glass.

[0026] [Optical glass]

[0027] The following is an explanation of the scope of each component (ingredient) constituting the optical glass of the present invention. In this specification, unless otherwise specified, the content of the cationic component is expressed as the molar percentage (mol%) of the cation in the total cationic component, and the content of the anionic component is expressed as the molar percentage (mol%) of the anion in the total anionic component; the ratio between the contents of the cationic components is the ratio of the molar percentage contents of the contents of the various cationic components.

[0028] Unless otherwise indicated in specific circumstances, the numerical ranges listed herein include upper and lower limits, "above" and "below" include the endpoints, and all integers and fractions included in the range, without being limited to the specific values ​​listed when the range is defined. "And / or" referred to herein is inclusive, for example, "A and / or B" means only A, or only B, or both A and B.

[0029] It should be noted that the ionic valences of the components described below are representative values ​​used for convenience and are not different from other ionic valences. The ionic valences of the components in the optical glass may be other than the representative values. For example, P usually exists in the glass in a state of +5 ionic valence, so in this disclosure, “P 5+ " is used as a representative value, but there is the possibility of existing in other ionic valence states, which is also within the scope of protection of the present disclosure.

[0030] <Cationic component>

[0031] P 5+It is a component of the optical glass of the present invention, and has the effect of inhibiting the devitrification of the glass and inhibiting the increase of density. When its content is less than 7%, the devitrification resistance of the glass decreases and the density increases. When its content exceeds 27%, the Abbe number of the glass decreases and the cost increases. Therefore, P in the present invention 5+ The content of is 7 to 27%, preferably 11 to 24%, more preferably 15 to 20%.

[0032] Al 3+ It can improve the stability of glass, and effectively improve the processability and chemical stability of glass, and at the same time increase the viscosity of glass during the molding process. 3+ When the content of Al is less than 10%, a stable glass skeleton cannot be formed and the above-mentioned effects cannot be obtained; 3+ When the content of Al is higher than 45%, the transition temperature and liquidus temperature of the glass increase, making melting difficult. At the same time, the temperature during molding increases, causing the volatilization of the glass to intensify, making the glass stripes worse, which is not conducive to large-diameter molding; on the other hand, too high a transition temperature makes compression molding difficult. Therefore, in the present invention, Al 3+ The content of is 10 to 45%, preferably 18 to 40%, and more preferably 24 to 35%.

[0033] Ba 2+ It has the effect of improving the refractive index, thermal stability and weather resistance of glass, but too much Ba 2+ This will increase the density of the glass and make it worse in abrasiveness, and reduce the viscosity, which will lead to worse stripes during molding, making it difficult to obtain large-diameter high-quality optical glass. 2+ The content of is 5 to 25%, preferably 9 to 21%, and more preferably 12 to 19%.

[0034] Sr 2+ It can reduce the thermal expansion coefficient of glass, and can effectively adjust the refractive index and density of glass, increase the viscosity of glass and improve the molding stripes. However, if its content is too high, the devitrification resistance and chemical stability of glass will be reduced. 2+ The content is 5 to 25%, preferably 8 to 21%, and more preferably 11 to 17%.

[0035] Ca 2+ It has the effect of increasing the viscosity of the glass, improving the molding stripes, and can improve the chemical stability of the glass and improve the glass grinding performance. However, if its content is too high, the refractive index of the glass is difficult to meet the design requirements, and the devitrification resistance may deteriorate. Therefore, in the present invention, Ca 2+ The content of is 5 to 30%, preferably 10 to 25%, more preferably 15 to 20%.

[0036] After extensive research by the inventors, it was found that in some embodiments, by controlling (Ba 2+ +Sr 2+ +Ca 2+ ) / Ba 2+ When the ratio is above 2.0, the viscosity of the glass liquid in the forming stage can be well controlled, the stability of the glass can be increased, and large-diameter optical glass with good stripe state can be obtained; but when (Ba 2+ +Sr 2+ +Ca 2+ ) / Ba 2+ When it is greater than 4.6, the devitrification resistance of the glass decreases sharply and it is difficult to form. 2+ +Sr 2+ +Ca 2+ ) / Ba 2+ It is 2.0 to 4.6, more preferably 2.5 to 4.1, and further preferably 3.0 to 3.9.

[0037] Mg 2+ It can improve the abrasiveness of glass, increase the viscosity of glass and improve the molding stripes. However, when its content is greater than 15%, the thermal stability of glass is greatly reduced. 2+ The content of is 0 to 15%, preferably 0 to 10%, and more preferably 0 to 5%.

[0038] In some embodiments, by controlling Mg 2+ The content of Al 3+ The ratio between the content of Mg 2+ / Al 3+ When the value is below 0.5, the anti-crystallization performance of the glass can be improved, so that the glass can obtain excellent production performance. 2+ / Al 3+ 0 to 0.5, more preferably Mg 2+ / Al 3+ 0 to 0.3, more preferably Mg 2+ / Al 3+ It is 0 to 0.1.

[0039] The inventors have found through a large number of experimental studies that in some embodiments, by controlling Al 3 The maximum content of 45% with Al 3+ The actual content of the difference is 45% -Al 3+ With Mg 2+ Maximum content 15% with Mg 2+ The difference in actual content is 15%-Mg 2+ The ratio between (45% -Al 3+ ) / (15%-Mg 2+), can effectively control the thermal stability (anti-crystallization performance) of the glass when it is reheated. 3+ ) / (15%-Mg 2+ ) is below 5.0, the thermal stability of the glass can be greatly optimized, and large-diameter stable pressing can be achieved; but when (45%-Al 3+ ) / (15%-Mg 2+ ) is less than 0.3, the anti-crystallization performance of the glass deteriorates, the liquidus temperature increases, and the difficulty of glass production increases. Therefore, it is preferred that (45%-Al 3+ ) / (15%-Mg 2+ ) is 0.3 to 5.0, more preferably (45%-Al 3 + ) / (15%-Mg 2+ ) is 0.4 to 4.0, and more preferably (45%-Al 3+ ) / (15%-Mg 2+ ) is 0.5 to 3.0, and more preferably (45%-Al 3+ ) / (15%-Mg 2+ ) is 0.6~2.0.

[0040] Al 3+ Mg 2+ In fluorophosphate glass, it has the function of forming a network and increasing the viscosity of the glass liquid, but it also causes the glass liquid phase temperature to rise. 2+ The devitrification resistance of the glass liquid can be improved while adjusting the glass viscosity. 3+ +Mg 2+ with Ba 2+ The ratio of (Al 3+ +Mg 2+ ) / Ba 2+ When the viscosity is below 3.5, fluorophosphate glass with suitable viscosity and good resistance to devitrification can be obtained; when (Al 3+ +Mg 2+ ) / Ba 2+ When it is less than 1.5, the viscosity of the glass liquid is too low, resulting in a narrower molding range and worse stripes, which is not conducive to large-diameter molding. 3+ +Mg 2+ ) / Ba 2+ 1.5 to 3.5, more preferably (Al 3+ +Mg 2+ ) / Ba 2+ is 2.0 to 3.0, and more preferably (Al 3+ +Mg 2+ ) / Ba 2+ It is 2.3 to 2.7.

[0041] Y 3+ It can increase the refractive index of glass and reduce the thermal expansion coefficient. If its content is higher than 10%, the liquidus temperature of the glass will rise, the devitrification resistance will decrease, the material will become shorter, and the control difficulty of large-diameter molding will increase. Therefore, Y 3+ The content is 0 to 10%, preferably 0 to 5%, and more preferably 0 to 3%.

[0042] La 3+ It has the effect of increasing the refractive index of glass and improving acid resistance. 3+ When the content of La is too high, the thermal stability and resistance to devitrification of the glass decrease, and the glass is prone to devitrification during the manufacturing process. 3+ The content is 0 to 10%, preferably 0 to 5%, and more preferably 0 to 2%.

[0043] G 3+ It can improve the stability of glass, and maintain low dispersion while appropriately increasing the refractive index, while appropriately increasing the mechanical strength and reducing the thermal expansion coefficient. If its content exceeds 10%, the resistance to devitrification of the glass will decrease. 3+ The content is 0 to 10%, preferably 0 to 5%, and more preferably 0 to 3%.

[0044] R + (R + For Li + 、Na + , K + One or more of these can effectively reduce the glass transition temperature, but R + The content of R is greater than 10%, which will increase the liquidus temperature of the glass and reduce the viscosity, making it difficult to form. + The content of R is 0 to 10%, preferably 0 to 6%, and more preferably 0 to 3%. + .

[0045] After a lot of experimental studies, it was found that in some embodiments, when Al 3+ The maximum content of 45% with Al 3+ The actual content of the difference is 45% -Al 3+ With the easy crystallization component Gd 3+ , Y 3+ ,La 3+ , Li + Total content of Gd 3+ +Y 3+ +La 3+ +Li + The ratio between (45% -Al 3+ ) / (Gd 3+ +Y 3+ +La3+ +Li + ) is greater than 2.0, it is easier to obtain glass with low crystallization tendency and good stripe state; but when (45%-Al 3+ ) /

[0046] (Gd 3+ +Y 3+ +La 3+ +Li + ) is greater than 80.0, the coloring degree of the glass increases, the stripe state becomes worse, and even difficult to form. Therefore, it is preferred that (45%-Al 3+ ) / (Gd 3+ +Y 3+ +La 3+ +Li + ) is 2.0 to 80.0, more preferably (45%-Al 3+ ) / (Gd 3 + +Y 3+ +La 3+ +Li + ) is 6.0 to 50.0, and more preferably (45%-Al 3+ ) / (Gd 3+ +Y 3+ +La 3+ +Li + ) is 8.0~35.0.

[0047] In some embodiments, by controlling Al 3+ The content of Mg 2+ , Li + The difference in content Al 3+ -Mg 2+ -Li + With P 5+ The ratio between the contents of Al 3+ -Mg 2+ -Li + ) / P 5+ In the range of 0.5 to 2.5, the desired optical properties can be easily obtained while improving the anti-crystallization performance of the glass. 3+ -Mg 2+ -Li + ) / P 5+ is 0.5 to 2.5, more preferably (Al 3+ -Mg 2 + -Li + ) / P 5+ is 1.0 to 2.3, and more preferably (Al 3+ -Mg 2+ -Li+ ) / P 5+ It is 1.3 to 2.1.

[0048] The optical glass of the present invention can contain less than 1% Sb 3+ As a clarifier to improve the clarification effect of glass, Sb is preferred. 3+ The content is 0 to 0.5%, more preferably 0 to 0.3%.

[0049] Without impairing the excellent properties of the glass of the present invention, the optical glass of the present invention may contain Ta, 5+ , W 6+ ,Ge 4+ 、Bi 3+ 、Te 4+ And other components.

[0050] <Anion component>

[0051] F - It has a significant effect on reducing the refractive index, temperature coefficient of refractive index and transition temperature of glass, and is an important component for increasing the Abbe number and abnormal dispersion. - If the content is too high, it will weaken the stability of the glass, increase the thermal expansion coefficient and abrasion, especially during the melting process. - The volatilization of F will not only pollute the environment, but also make the optical constants of the glass exceed the design range. - If the content of F is less than 50%, it is difficult to obtain the designed Abbe number and abnormal dispersion. - If the content of F is higher than 90%, the Abbe number of the glass will become too large, and the volatilization will increase sharply during melting and precision molding. - The content of is 50 to 90%, preferably 60 to 80%, more preferably 67 to 75%.

[0052] The optical glass of the present invention contains O 2- , especially by containing more than 10% O 2- , can obtain excellent optical properties and low wear. 2- When the content of O is greater than 50%, the liquidus temperature of the glass rises rapidly. 2- The content of is 10 to 50%, preferably 20 to 40%, more preferably 25 to 33%.

[0053] The optical glass of the present invention can be prepared by containing less than 1% Cl - As a clarifier to improve the clarification effect of glass, Cl is preferred. - The content is 0 to 0.5%, more preferably 0 to 0.3%.

[0054] <Ingredients that should not be contained>

[0055] Without impairing the excellent properties of the glass of the present invention, other components not mentioned above can be added as needed. However, transition metal components such as Ce, V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo, even if contained in small amounts alone or in combination, will color the glass and produce absorption at specific wavelengths in the visible light region, thereby weakening the property of improving the visible light transmittance of the present invention. Therefore, it is preferred that the optical glass, especially for optical glass with required transmittance at wavelengths in the visible light region, substantially does not contain the above components.

[0056] The cations of Pb, Th, Cd, Tl, Os, Be and Se have a tendency to be controlled in recent years as harmful chemical substances, and environmental protection measures are necessary not only in the manufacturing process of glass, but also in the processing process and the disposal after productization. Therefore, in the case of paying attention to the impact on the environment, it is preferred that they are not actually contained except for the inevitable mixing. Thus, the optical glass does not actually contain substances that pollute the environment. Therefore, even if no special environmental countermeasures are taken, the optical glass of the present invention can be manufactured, processed and discarded.

[0057] The "does not contain" and "0%" recorded in this article mean that the component is not intentionally added as a raw material to the optical glass of the present invention; however, as raw materials and / or equipment for producing optical glass, there will be certain impurities or components that are not intentionally added, which will be contained in a small amount or trace amount in the final optical glass, and this situation is also within the scope of protection of the patent of this invention.

[0058] Next, the properties of the optical glass of the present invention will be described.

[0059] <Refractive Index and Abbe Number>

[0060] The refractive index of optical glass (n d ) and the Abbe number (ν d ) Tested according to the method specified in GB / T 7962.1-2010.

[0061] In some embodiments, the refractive index (n d ) is 1.46 to 1.52, and preferably the refractive index (n d ) is 1.47 to 1.51, and the refractive index (n d ) is 1.48~1.50.

[0062] In some embodiments, the Abbe number (ν d ) is 81 to 89, preferably the Abbe number (ν d ) is 83 to 88, and more preferably the Abbe number (ν d) is 84~87.

[0063] <Color>

[0064] The short-wave transmission spectrum characteristics of the optical glass of the present invention are expressed by the coloring degree (λ 80 / λ5). 80 It refers to the wavelength when the glass transmittance reaches 80%, and λ5 refers to the wavelength when the glass transmittance reaches 5%. 80 The measurement is to use a glass with a thickness of 10±0.1mm and two parallel and optically polished opposite planes, and measure the spectral transmittance in the wavelength range from 280nm to 700nm and the wavelength at which the transmittance is 80%. The so-called spectral transmittance or transmittance refers to the wavelength at which the incident intensity I is perpendicular to the above surface of the glass. in Light of intensity I passes through the glass and is emitted from another plane out In the case of light, through I out / I in λ is a quantity expressed by λ, and also includes the transmittance of the surface reflection loss on the above-mentioned surface of the glass. In the glass of the present invention, λ 80 A small value of means that the glass itself is less colored. The same is true for λ5.

[0065] In some embodiments, the λ of the optical glass of the present invention is 80 Less than or equal to 340nm, preferably λ 80 Less than or equal to 335nm, more preferably λ 80 Less than or equal to 330nm, more preferably λ 80 Less than or equal to 325nm, more preferably λ 80 Less than or equal to 320nm.

[0066] In some embodiments, the λ5 of the optical glass of the present invention is less than or equal to 265 nm, preferably λ5 is less than or equal to 260 nm, more preferably λ5 is less than or equal to 255 nm, further preferably λ5 is less than or equal to 250 nm, and further preferably λ5 is less than or equal to 245 nm.

[0067] <density>

[0068] The density (ρ) of optical glass is measured according to the method specified in GB / T 7962.20-2010 and is the mass per unit volume at 20°C in g / cm 3 express.

[0069] In some embodiments, the density (ρ) of the optical glass of the present invention is 3.90 g / cm 3 Below, preferably 3.82 g / cm 3 Below, more preferably 3.78g / cm3 Below, more preferably 3.74 g / cm 3 the following.

[0070] <Transition Temperature>

[0071] Transition temperature of optical glass (T g ) Tested according to the method specified in GB / T 7962.16-2010.

[0072] In some embodiments, the transition temperature (T g ) is 500°C or lower, preferably 490°C or lower, more preferably 480°C or lower.

[0073] <Acid resistance stability>

[0074] The acid resistance (RA) (surface method) of optical glass is tested according to the method specified in GB / T 7962.14-2010.

[0075] In some embodiments, the acid resistance stability (RA) of the optical glass of the present invention is Class 3 or higher, preferably Class 2 or higher.

[0076] <Moisture resistance stability>

[0077] The moisture resistance stability (RC) (surface method) of optical glass is tested according to the method specified in GB / T 7962.15-2010.

[0078] In some embodiments, the optical glass of the present invention has a moisture resistance stability (RC) of Class 2 or above, preferably Class 1.

[0079] <Striation Degree>

[0080] The glass was formed into a specification of 200mm in width and 30mm in thickness, and a glass blank was obtained by cutting it into pieces every 360mm in length, that is, the size of the blank was 200mm in width*thickness*length×30mm×360mm. The glass blank was processed into a sample of 200mm in width×thickness×length×80mm, and the two end faces of the sample along the length direction were polished to obtain a stripe test sample.

[0081] The streak degree of glass is checked by comparing with the standard sample from the direction where the streaks are most easily seen using a streak meter consisting of a point light source and a lens. It is divided into 4 levels, as shown in Table 1 below.

[0082] Table 1. Streak level table

[0083] grade Streak degree A Under the specified testing conditions, there are no stripes visible to the naked eye inside and the edge stripes are less than 2mm. B Under the specified testing conditions, there are no stripes visible to the naked eye inside, and the edge stripes are 2-4mm. C There are slight parallel streaks under the specified test conditions. D There are roughly parallel stripes under the specified test conditions.

[0084] In some embodiments, when the glass molding thickness is greater than 20 mm, the striae of the optical glass of the present invention is above grade C, preferably above grade B, and more preferably grade A, and has excellent large-diameter molding performance.

[0085] <Anti-crystallization performance>

[0086] The anti-crystallization performance test method of the optical glass of the present invention is as follows: a glass sample of 10 mm × 20 mm × 20 mm is placed in a semicircular porcelain box with a radius of 15 mm and a depth of 15 mm, and the glass sample and the porcelain box are placed in a T g The first heating is carried out in a test furnace of + (140-160°C) for 15 minutes, and then the temperature is lowered to 200°C in a tunnel annealing furnace; then the temperature is stabilized at T g + (140 ~ 160 ℃) test furnace for the second heating, the heating time is 15 minutes, and then taken out and cooled to 200 ℃ again in the tunnel annealing furnace. After the second heating, the glass sample and the porcelain box are placed in the tunnel annealing furnace and cooled to 200 ℃. After taking out the glass sample, it is naturally cooled to room temperature in the atmosphere. After grinding and polishing the glass sample, the overall softening degree and devitrification of the glass are observed by naked eyes, and the inside of the glass is observed under a microscope to confirm the existence of crystallization particles. According to the following Table 2, the anti-crystallization performance of the glass is judged, with grade A being the best and grade E being the worst.

[0087] Table 2. Classification and judgment criteria of anti-crystallization performance

[0088]

[0089] In some embodiments, the anti-crystallization performance of the optical glass of the present invention is above grade D, preferably above grade C, more preferably grade B, and further preferably grade A, and has excellent thermal stability that can be used for large-diameter pressing.

[0090] [Method for producing optical glass]

[0091] The manufacturing method of the optical glass of the present invention is as follows: the optical glass of the present invention is produced by conventional raw materials and conventional processes, using carbonates, nitrates, sulfates, phosphates, oxides, fluorides, metaphosphates, etc. as raw materials, and after the materials are prepared according to the conventional method, the prepared furnace materials are put into a melting furnace at 900-1000° C. for melting, and after clarification and sufficient homogenization, the optical glass of the present invention is obtained by pouring or leaking at a temperature below 800° C. Those skilled in the art can appropriately select raw materials, process methods and process parameters according to actual needs.

[0092] [Glass preforms and optical components]

[0093] The glass preform can be made from the produced optical glass by means of grinding, or by means of press molding such as re-hot pressing, precision stamping, etc. That is, the glass preform can be made by mechanical processing such as grinding and polishing the optical glass, or by making a preform for press molding from the optical glass, re-hot pressing the preform and then grinding the preform to make the glass preform, or by precision stamping the preform produced by grinding.

[0094] It should be noted that the means for preparing the glass preform is not limited to the above means. As described above, the optical glass of the present invention is useful for various optical elements and optical designs, and it is particularly preferred to form a preform from the optical glass of the present invention, and use the preform to perform re-hot pressing, precision stamping, etc. to make optical elements such as lenses and prisms.

[0095] The glass preform and the optical element of the present invention are both formed of the optical glass of the present invention. The glass preform of the present invention has the excellent properties of optical glass, and the optical element of the present invention has the excellent properties of optical glass. Examples of lenses include various lenses such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses, which have spherical or aspherical lens surfaces.

[0096] [Optical instruments]

[0097] The optical element formed by the optical glass of the present invention can be used to manufacture optical instruments such as photographic equipment, video equipment, display equipment and monitoring equipment.

[0098] Example

[0099] <Optical Glass Example>

[0100] In order to further clearly illustrate and describe the technical solutions of the present invention, the following non-limiting examples are provided.

[0101] This embodiment adopts the above optical glass manufacturing method to obtain optical glasses having the compositions shown in Tables 3 to 5. In addition, the properties of each glass are measured by the testing method described in the present invention, and the measurement results are shown in Tables 3 to 5.

[0102] Table 3.

[0103]

[0104]

[0105] Table 4.

[0106]

[0107]

[0108] Table 5.

[0109]

[0110]

[0111] <Glass Preform Example>

[0112] The glasses obtained from the optical glass examples 1 to 22# are processed by means of grinding, or by means of molding such as hot pressing, precision stamping, etc., to make preforms of various lenses, prisms, etc., such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, plano-concave lenses, etc. Under the original molding process, there are no crystallization particles in the molded products, which greatly improves the molding efficiency and the product yield.

[0113] <Optical Element Embodiment>

[0114] The preforms obtained in the above-mentioned glass preform embodiments are annealed to reduce the internal stress of the glass and fine-tune the refractive index so that the optical properties such as the refractive index reach the desired values.

[0115] Next, each preform is ground and polished to produce various lenses and prisms such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses. The surface of the obtained optical element may be coated with an anti-reflection film.

[0116] The optical glass obtained in Examples 1 to 22# is cut into predetermined sizes, and the blanks are subjected to optical cold processing such as grinding and polishing to obtain large-diameter, high-quality optical elements. The surface of the obtained optical element can also be coated with an anti-reflection film.

[0117] <Optical Instrument Embodiment>

[0118] The optical element obtained by the above-mentioned optical element embodiment is optically designed to form an optical component or optical assembly by using one or more optical elements, and can be used in, for example, imaging equipment, sensors, microscopes, medical technology, digital projection, communications, optical communication technology / information transmission, optics / lighting in the automotive field, lithography technology, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips.

Claims

1. Optical glass, characterized in that: Its components are expressed in molar percentage, and the cationic component contains: P 5+ :7~27%;Al 3+ :10~45%;Ba 2+ :5~25%; Sr 2+ :5~25%;Ca 2+ :5~30%, The anionic component contains: F - :50~90%;O 2- :10~50%.

2. The optical glass according to claim 1, characterized in that: Its components are expressed in molar percentages, and the cationic components also contain: Mg 2+ :0~15%;and / or Y 3+ : 0-10%; and / or La 3+ :0~10%;and / or Gd 3+ :0~10%;and / or R + :0~10%;and / or Sb 3+ :0~1%,the R + For Li + 、Na + , K + One or more of .

3. The optical glass according to claim 1, characterized in that: Its components are expressed in molar percentages, and the anion components also contain: Cl - :0~1%.

4. Optical glass, characterized in that: Its components are expressed in molar percentage, and the cationic component is represented by P 5+ :7~27%;Al 3+ :10~45%;Ba 2+ :5~25%; Sr 2+ :5~25%;Ca 2+ :5~30%;Mg 2+ :0~15%;Y 3+ :0~10%; La 3+ :0~10%;Gd 3+ :0~10%;R + :0~10%; Sb 3+ : 0~1% composition, the R + For Li + 、Na + , K + One or more of the anion component is F - :50~90%;O 2- :10~50%;Cl - : 0~1% composition.

5. The optical glass according to any one of claims 1 to 4, characterized in that: Its components are expressed in mole percentage and meet one or more of the following four conditions: 1)(Ba 2+ +Sr 2+ +Ca 2+ ) / Ba 2+ 2.0 to 4.6, preferably 2.5 to 4.1, more preferably 3.0 to 3.9; 2)(45%-Al 3+ ) / (15%-Mg 2+ ) is 0.3 to 5.0, preferably (45%-Al 3+ ) / (15%-Mg 2+ ) is 0.4 to 4.0, more preferably (45%-Al 3+ ) / (15%-Mg 2+ ) is 0.5 to 3.0, and more preferably (45%-Al 3+ ) / (15%-Mg 2+ ) is 0.6~2.0; 3)(Al 3+ +Mg 2+ ) / Ba 2+ 1.5 to 3.5, preferably (Al 3+ +Mg 2+ ) / Ba 2+ 2.0 to 3.0, more preferably (Al 3+ +Mg 2+ ) / Ba 2+ 2.3~2.7; 4)(45%-Al 3+ ) / (Gd 3+ +Y 3+ +La 3+ +Li + ) is 2.0 to 80.0, preferably (45%-Al 3+ ) / (Gd 3+ +Y 3+ +La 3+ +Li + ) is 6.0 to 50.0, more preferably (45%-Al 3+ ) / (Gd 3+ +Y 3+ +La 3+ +Li + ) is 8.0~35.

0.

6. The optical glass according to any one of claims 1 to 4, characterized in that: Its components are expressed in molar percentage, among which: Mg 2+ / Al 3+ 0 to 0.5, preferably Mg 2+ / Al 3+ 0 to 0.3, more preferably Mg 2+ / Al 3+ 0 to 0.1; and / or (Al 3+ -Mg 2 + -Li + ) / P 5+ 0.5 to 2.5, preferably (Al 3+ -Mg 2+ -Li + ) / P 5+ is 1.0 to 2.3, more preferably (Al 3+ -Mg 2+ -Li + ) / P 5+ It is 1.3 to 2.

1.

7. The optical glass according to any one of claims 1 to 4, characterized in that: Its components are expressed in molar percentage, where: P 5+ : 11-24%, preferably P 5+ : 15-20%; and / or Al 3+ : 18-40%, preferably Al 3+ : 24-35%; and / or Ba 2+ : 9-21%, preferably Ba 2+ :12~19%;and / or Sr 2+ : 8-21%, preferably Sr 2+ :11~17%;and / or Ca 2+ : 10-25%, preferably Ca 2+ :15~20%;and / or Mg 2+ : 0-10%, preferably Mg 2+ :0~5%;and / or Y 3+ : 0-5%, preferably Y 3 + : 0-3%; and / or La 3+ : 0-5%, preferably La 3+ :0~2%;and / or Gd 3+ : 0-5%, preferably Gd 3+ :0~3%;and / or R + : 0~6%, preferably R + : 0 to 3%, preferably no R + ; and / or Sb 3+ : 0~0.5%, preferably Sb 3+ :0~0.3%,the R + For Li + 、Na + , K + One or more of .

8. The optical glass according to any one of claims 1 to 4, characterized in that: Its components are expressed in mole percentages, where: F - : 60 to 80%, preferably F - : 67 to 75%; and / or O 2- : 20 to 40%, preferably O 2- : 25 to 33%; and / or Cl - : 0 to 0.5%, preferably Cl - : 0 to 0.3%.

9. The optical glass according to any one of claims 1 to 4, characterized in that: The refractive index n of the optical glass d The refractive index n is preferably 1.46 to 1.

52. d The refractive index n is preferably 1.47 to 1.

51. d 1.48~1.50; Abbe number ν d 81 to 89, preferably Abbe number ν d 83 to 88, more preferably Abbe number ν d It is 84 to 87.

10. The optical glass according to any one of claims 1 to 3, characterized in that: The λ of the optical glass 80 Less than or equal to 340nm, preferably λ 80 Less than or equal to 335nm, more preferably λ 80 Less than or equal to 330nm, more preferably λ 80 Less than or equal to 325nm, more preferably λ 80 less than or equal to 320nm; and / or λ5 is less than or equal to 265nm, preferably λ5 is less than or equal to 260nm, more preferably λ5 is less than or equal to 255nm, further preferably λ5 is less than or equal to 250nm, and further preferably λ5 is less than or equal to 245nm; and / or density ρ is 3.90g / cm 3 Below, the preferred density ρ is 3.82 g / cm 3 Below, the more preferred density ρ is 3.78 g / cm 3 Below, the density ρ is further preferably 3.74 g / cm 3 Below; and / or transition temperature T g The preferred transition temperature is 500°C or less. g The transition temperature is preferably 490°C or less. g is below 480°C; and / or acid resistance stability RA is Class 3 or above, preferably acid resistance stability RA is Class 2 or above; and / or moisture resistance stability RC is Class 2 or above, preferably moisture resistance stability RC is Class 1; and / or the stripe degree is Class C or above, preferably the stripe degree is Class B or above, and more preferably the stripe degree is Class A; and / or the anti-crystallization performance is Class D or above, preferably the anti-crystallization performance is Class C or above, more preferably the anti-crystallization performance is Class B, and further preferably the anti-crystallization performance is Class A.

11. A glass preform, characterized in that: Made of the optical glass described in any one of claims 1 to 10.

12. An optical element, characterized in that The optical glass is made of any one of claims 1 to 10, or the glass preform is made of claim 11.

13. An optical instrument, characterized in that Contains the optical glass according to any one of claims 1 to 10, and / or contains the optical element according to claim 12.

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