CN113264675A

CN113264675A - Optical glass, optical element and optical instrument

Info

Publication number: CN113264675A
Application number: CN202110706403.8A
Authority: CN
Inventors: 匡波
Original assignee: CDGM Glass Co Ltd
Current assignee: CDGM Glass Co Ltd
Priority date: 2021-06-24
Filing date: 2021-06-24
Publication date: 2021-08-17
Anticipated expiration: 2041-06-24
Also published as: CN113264675B

Abstract

The invention provides an optical glass, which comprises the following components in percentage by weight: SiO 2₂：23～45％；Nb₂O₅：20～40％；ZrO₂：2～14％；BaO：2～18％；Li₂O：1～12％；La₂O₃: 0 to 14% of Nb₂O₅/(BaO+La₂O₃) Is 0.8 to 8.0. Through reasonable component design, the optical glass obtained by the invention has low relative partial dispersion, negative anomalous dispersion and excellent secondary compression anti-crystallization performance, and meets the application of high-end photoelectric products.

Description

Optical glass, optical element and optical instrument

Technical Field

The invention relates to optical glass, in particular to optical glass with a refractive index of 1.69-1.82 and an Abbe number of 32-40, and an optical element and an optical instrument made of the optical glass.

Background

The optical glass is an important component of photoelectric products, and in recent years, with the rapid development of photoelectric products such as smart phones, single-lens reflex cameras, monitoring security and the like, higher requirements are put forward on the performance of the optical glass. For example, in optical design, it is desirable that the optical glass has a property of eliminating or eliminating as much as possible the residual chromatic aberration of the secondary spectrum, which requires that the optical glass has a certain anomalous dispersion along with a desired refractive index, abbe number.

Refractive index (n)_d) At 1.69-1.82 Abbe number (v)_d) The optical glass within the range of 32-40 belongs to flint optical glass, and can be widely applied to various optical systems. In the prior art, the optical glass in the range has high relative partial dispersion and no anomalous dispersion, and is difficult to meet the requirement of eliminating residual chromatic aberration of a secondary spectrum, for example, the optical glass disclosed in the patent with the publication number of CN103086599A has the refractive index of 1.75-1.77 and AbbeThe number of the optical glasses is 39 to 41. On the other hand, the mainstream manufacturing method of the glass preform and the optical element is the secondary hot press molding, and if the secondary press type devitrification resistance of the optical glass is poor, crystals or opacification is easily generated in the hot press manufacturing process of the glass preform or the glass element, and the application to a high-precision optical instrument is difficult.

Therefore, the development of the optical glass which has the refractive index of 1.69-1.82, the Abbe number of 32-40, relatively low partial dispersion, negative anomalous dispersion and excellent secondary compression crystallization resistance is of great significance for the development of the photoelectric field.

Disclosure of Invention

The invention aims to solve the technical problem of providing the optical glass which has low dispersion of opposite parts, negative anomalous dispersion and excellent secondary compression anti-crystallization performance.

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

the optical glass comprises the following components in percentage by weight: SiO 2₂：23～45％；Nb₂O₅：20～40％；ZrO₂：2～14％；BaO：2～18％；Li₂O：1～12％；La₂O₃: 0 to 14% of Nb₂O₅/(BaO+La₂O₃) Is 0.8 to 8.0.

Further, the optical glass comprises the following components in percentage by weight: ZnO: 0 to 10 percent; and/or CaO: 0 to 18 percent; and/or SrO: 0-8%; and/or MgO: 0-8%; and/or Na₂O: 0 to 10 percent; and/or K₂O: 0-8%; and/or Gd₂O₃: 0 to 10 percent; and/or Y₂O₃: 0 to 10 percent; and/or Yb₂O₃: 0 to 10 percent; and/or WO₃: 0 to 5 percent; and/or B₂O₃: 0-8%; and/or TiO₂: 0 to 5 percent; and/or Al₂O₃: 0 to 5 percent; and/or Ta₂O₅: 0 to 5 percent; and/or a clarifying agent: 0-1% of a clarifying agent Sb₂O₃、SnO、SnO₂、CeO₂One or more ofAnd (4) seed preparation.

Optical glass, the composition of which is expressed in weight percentage by SiO₂：23～45％；Nb₂O₅：20～40％；ZrO₂：2～14％；BaO：2～18％；Li₂O：1～12％；La₂O₃：0～14％；ZnO：0～10％；CaO：0～18％；SrO：0～8％；MgO：0～8％；Na₂O：0～10％；K₂O：0～8％；Gd₂O₃：0～10％；Y₂O₃：0～10％；Yb₂O₃：0～10％；WO₃：0～5％；B₂O₃：0～8％；TiO₂：0～5％；Al₂O₃：0～5％；Ta₂O₅: 0 to 5 percent; a clarifying agent: 0 to 1% of Nb₂O₅/(BaO+La₂O₃) 0.8-8.0, and the clarifying agent is Sb₂O₃、SnO、SnO₂、CeO₂One or more of (a).

Further, the optical glass comprises the following components in percentage by weight: nb₂O₅/(BaO+La₂O₃) 1.0 to 6.0; and/or ZnO/(BaO + La)₂O₃) Is 2.0 or less; and/or (CaO + Na)₂O)/BaO is 0.02-8.0; and/or BaO/(Na)₂O+Nb₂O₅) 0.05 to 0.8; and/or SiO₂/Nb₂O₅0.65 to 2.0; and/or Li₂O/(Li₂O+Na₂O+K₂O) is 0.3 to 1.0; and/or SiO₂V (BaO + ZnO) is 1.0-20.0; and/or B₂O₃/SiO₂Is 0.3 or less.

Further, the optical glass comprises the following components in percentage by weight: nb₂O₅/(BaO+La₂O₃) 1.2 to 4.0; and/or ZnO/(BaO + La)₂O₃) 0.05 to 1.5; and/or (CaO + Na)₂O)/BaO is 0.05 to 5.0; and/or BaO/(Na)₂O+Nb₂O₅) 0.1 to 0.6; and/or SiO₂/Nb₂O₅0.75 to 1.8; and/or Li₂O/(Li₂O+Na₂O+K₂O) is 0.4 to 0.9; and/or SiO₂V (BaO + ZnO) is 1.5-15.0; and/or B₂O₃/SiO₂Is 0.2 or less.

Further, the optical glass comprises the following components in percentage by weight: nb₂O₅/(BaO+La₂O₃) 1.5 to 3.0; and/or ZnO/(BaO + La)₂O₃) 0.08 to 1.0; and/or (CaO + Na)₂O)/BaO is 0.1 to 3.0; and/or BaO/(Na)₂O+Nb₂O₅) 0.15 to 0.5; and/or SiO₂/Nb₂O₅0.8 to 1.5; and/or Li₂O/(Li₂O+Na₂O+K₂O) is 0.45 to 0.8; and/or SiO₂V (BaO + ZnO) is 2.0-10.0; and/or B₂O₃/SiO₂Is 0.15 or less.

Further, the optical glass comprises the following components in percentage by weight: ZnO/(BaO + La)₂O₃) 0.1 to 0.5; and/or (CaO + Na)₂O)/BaO is 0.2 to 1.0; and/or BaO/(Na)₂O+Nb₂O₅) 0.2 to 0.4; and/or SiO₂/Nb₂O₅0.9 to 1.3; and/or Li₂O/(Li₂O+Na₂O+K₂O) is 0.5 to 0.75; and/or SiO₂V (BaO + ZnO) is 2.5-5.0; and/or B₂O₃/SiO₂Is 0.1 or less.

Further, the optical glass comprises the following components in percentage by weight: SiO 2₂: 28-42%, preferably SiO₂: 31-40%; and/or Nb₂O₅: 22 to 37%, preferably Nb₂O₅: 26 to 33 percent; and/or ZrO₂: 3 to 12%, preferably ZrO₂: 5-10%; and/or BaO: 4-15%, preferably BaO: 5-12%; and/or Li₂O: 1 to 10%, preferably Li₂O: 1-9%; and/or La₂O₃: 2-12%, preferably La₂O₃: 4-10%; and/or ZnO: 0.1-8%, preferably ZnO: 0.5-6%; and/or CaO: 0-16.5%, preferably CaO: 0-8%; andor SrO: 0 to 5%, preferably SrO: 0-2%; and/or MgO: 0-5%, preferably MgO: 0-2%; and/or Na₂O: 0.5-8%, preferably Na₂O: 1-6%; and/or K₂O: 0 to 5%, preferably K₂O: 0 to 4 percent; and/or Gd₂O₃: 0 to 5%, preferably Gd₂O₃: 0 to 3 percent; and/or Y₂O₃: 0 to 5%, preferably Y₂O₃: 0 to 3 percent; and/or Yb₂O₃: 0 to 5%, preferably Yb₂O₃: 0 to 3 percent; and/or WO₃: 0 to 3%, preferably WO₃: 0-2%; and/or B₂O₃: 0 to 4%, preferably B₂O₃: 0-2%; and/or TiO₂: 0 to 3%, preferably TiO₂: 0-2%; and/or Al₂O₃: 0 to 2%, preferably Al₂O₃: 0 to 1 percent; and/or Ta₂O₅: 0 to 2%, preferably Ta₂O₅: 0 to 1 percent; and/or a clarifying agent: 0-0.5%, the clarifying agent is Sb₂O₃、SnO、SnO₂、CeO₂One or more of (a).

Further, the optical glass does not contain B in the components₂O₃(ii) a And/or does not contain TiO₂(ii) a And/or does not contain WO₃(ii) a And/or does not contain Ta₂O₅(ii) a And/or does not contain SrO; and/or does not contain MgO; and/or does not contain CaO; and/or does not contain Gd₂O₃(ii) a And/or does not contain Y₂O₃。

Further, the refractive index n of the optical glass_d1.69 to 1.82, preferably 1.71 to 1.80, more preferably 1.72 to 1.77, still more preferably 1.73 to 1.76, and/or Abbe number v_dIs 32 to 40, preferably 33 to 38, and more preferably 34 to 37.

Further, the relative partial dispersion P of the optical glass_g,FIs 0.7000 or less, preferably 0.6500 or less, more preferably 0.6000 or less, and/or a relative partial dispersion deviation value Δ P_g,FLess than 0, preferably less than-0.0010, more preferably less than-0.0020, andthe content of the first step is preferably-0.0030 or less.

Further, the density rho of the optical glass is 3.80g/cm³Hereinafter, it is preferably 3.70g/cm³Hereinafter, more preferably 3.60g/cm³The following; and/or coefficient of thermal expansion alpha_-30/70℃Is 95X 10^-7Preferably 90X 10 or less,/K^-7A value of not more than 85X 10^-7below/K; and/or transition temperature T_g600 ℃ or lower, preferably 590 ℃ or lower, more preferably 580 ℃ or lower; and/or lambda₈₀Less than or equal to 410nm, preferably lambda₈₀Less than or equal to 400nm, more preferably lambda₈₀Less than or equal to 395 nm; and/or lambda₅Less than or equal to 340nm, preferably lambda₅Less than or equal to 335nm, more preferably lambda₅Less than or equal to 330 nm; 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 Knoop hardness H_KIs 530 x 10⁷Pa or more, preferably 550X 10⁷Pa or more, more preferably 570X 10⁷Pa or above.

The glass preform is made of the optical glass.

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

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

The invention has the beneficial effects that: through reasonable component design, the optical glass obtained by the invention has low relative partial dispersion, negative anomalous dispersion and excellent secondary compression anti-crystallization performance, and meets the application of high-end photoelectric products.

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.

[ optical glass ]

The ranges of the respective components (components) of the optical glass of the present invention are explained below. In the present invention, the contents and total contents of the respective components are all expressed in weight percent (wt%), that is, the contents and total contents of the respective components are expressed in weight percent with respect to the total amount of the glass substance converted into the composition of oxides, if not specifically stated. Here, the "composition converted to oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the optical glass composition component of the present invention are decomposed in the melt and converted to oxides, the total amount of the oxides is 100%.

Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means A alone, B alone, or both A and B.

< essential Components and optional Components >

SiO₂Has the effects of improving the chemical stability of glass, maintaining the viscosity suitable for the formation of molten glass and reducing the corrosion to refractory materials or platinum ware, and the invention contains more than 23 percent of SiO₂To obtain the above effects, SiO is preferable₂Is 28% or more, and SiO is more preferable₂The content of (B) is more than 31%. If SiO₂Too high content of (b) increases the difficulty of melting the glass, while being disadvantageous in lowering the transition temperature of the glass. Thus, SiO in the present invention₂The upper limit of the content of (B) is 45%, preferably 42%, more preferably 40%.

Nb₂O₅Is a high-refractive high-dispersion component, can improve the refractive index and devitrification resistance of the glass, and has the function of reducing the relative partial dispersion P of the glass_g,FAnd relative partial dispersion deviation value Δ P_g,FBy containing 20% or more of the above-mentioned componentsNb of₂O₅To obtain the above effects, Nb is preferable₂O₅The lower limit of (B) is 22%, and the more preferable lower limit is 26%. If Nb₂O₅More than 40%, the thermal and chemical stability of the glass is lowered and the light transmittance is lowered, so that Nb in the present invention is₂O₅The upper limit of the content of (B) is 40%, preferably 37%, more preferably 33%.

The inventors have discovered, through extensive experimental studies, that in some embodiments of the invention, SiO is controlled₂Content of (2) and Nb₂O₅Ratio between contents of (A) SiO₂/Nb₂O₅Within the range of 0.65 to 2.0, the optical glass of the present invention can obtain desired optical constants and reduce the P value of the glass_g,FValue sum Δ P_g,FAnd improve the chemical stability of the glass. Therefore, SiO is preferable₂/Nb₂O₅0.65 to 2.0, more preferably SiO₂/Nb₂O₅0.75 to 1.8, and more preferably SiO₂/Nb₂O₅0.8 to 1.5, and further preferably SiO₂/Nb₂O₅0.9 to 1.3.

ZrO₂Can improve the refractive index of the glass, adjust the dispersion and reduce the P of the glass_g,FValue sum Δ P_g,FThe alkali resistance of the glass is optimized by containing ZrO in an amount of 2% or more in the present invention₂In order to obtain the above effects, it is preferable to contain 3% or more of ZrO₂More preferably, it contains 5% or more of ZrO₂. If ZrO of₂The content of (b) is more than 14%, the difficulty of melting the glass increases, the melting temperature increases, and inclusions appear in the glass and the light transmittance decreases. Thus, ZrO₂The content of (b) is 14% or less, preferably 12% or less, more preferably 10% or less.

ZnO can adjust the refractive index and dispersion of glass, improve the stability of the glass, and simultaneously ZnO can reduce the high-temperature viscosity and the transition temperature of the glass, so that the glass can be smelted at a lower temperature, and the light transmittance of the glass is improved. On the other hand, if the content of ZnO is too high, the difficulty of glass forming increases, and the devitrification resistance becomes poor. Therefore, the content of ZnO is 10% or less, preferably 0.1 to 8%, more preferably 0.5 to 6%.

BaO in the present invention can improve devitrification resistance and hardness of the glass and reduce the temperature coefficient of refractive index and thermal expansion coefficient of the glass, and in the present invention, the above effects are obtained by containing BaO in an amount of 2% or more, preferably 4% or more, and more preferably 5% or more. On the other hand, by setting the BaO content to 18% or less, it is possible to prevent the decrease in chemical stability due to an excessively high BaO content, and the BaO content is preferably 15% or less, and more preferably 12% or less.

In some embodiments of the invention, SiO is controlled₂SiO is a ratio of the content of (B) to the total content of BaO and ZnO (BaO + ZnO)₂And/or (BaO + ZnO) is within the range of 1.0-20.0, so that the glass forming stability and the light transmittance of the glass can be optimized, and the thermal expansion coefficient of the glass can be reduced. Therefore, SiO is preferable₂/(BaO + ZnO) is 1.0 to 20.0, and SiO is more preferable₂/(BaO + ZnO) of 1.5 to 15.0, and SiO is more preferable₂/(BaO + ZnO) is 2.0 to 10.0, and SiO is more preferable₂and/(BaO + ZnO) is 2.5 to 5.0.

CaO contributes to adjustment of the optical constants of the glass and improvement of the processability of the glass, but when the content of CaO is too large, the optical constants of the glass do not meet the requirements, and the devitrification resistance is deteriorated. Therefore, the CaO content is in the range of 0 to 18%, preferably 0 to 16.5%, and more preferably 0 to 8%. In some embodiments, it is further preferred that CaO is absent.

While SrO can adjust the refractive index and dispersion of glass, if the content is too large, the chemical stability of glass is lowered and the cost of glass is also increased. Therefore, the SrO content is 0 to 8%, preferably 0 to 5%, and more preferably 0 to 2%. In some embodiments, it is further preferred that SrO is absent.

MgO is beneficial to reducing the density and melting temperature of the glass, but when the content of MgO is too much, the refractive index of the glass is difficult to meet the design requirement, and the anti-crystallization performance and the stability of the glass are reduced. Therefore, the MgO content is 0 to 8%, preferably 0 to 5%, and more preferably 0 to 2%. In some embodiments, it is further preferred that no MgO be present.

Li₂O can remarkably improve the meltability of the glass and increase ZrO₂Solubility in glass and lowering of glass transition temperature, adjusting of glass refractive index, but too high content thereof is disadvantageous in acid resistance stability and thermal expansion coefficient of glass. Thus, Li in the present invention₂The content of O is 1 to 12%, preferably 1 to 10%, more preferably 1 to 9%.

Na₂O has the effect of improving the meltability of the glass and lowering the glass transition temperature, and if the content exceeds 10%, the chemical stability of the glass is lowered. Thus, Na₂The content of O is 0 to 10%, preferably 0.5 to 8%, more preferably 1 to 6%.

In some embodiments of the invention, the composition is prepared by combining CaO and Na₂Total content of O (CaO + Na)₂Ratio between O) and BaO content (CaO + Na)₂The O)/BaO is within the range of 0.02-8.0, the chemical stability of the optical glass can be improved, the density of the glass can be reduced, and the light weight of an optical system can be realized. Therefore, (CaO + Na) is preferable₂O)/BaO is 0.02 to 8.0, and (CaO + Na) is more preferable₂O)/BaO is 0.05 to 5.0. Further, by reacting (CaO + Na)₂The O)/BaO is in the range of 0.1-3.0, and the hardness of the glass can be further optimized. Therefore, (CaO + Na) is more preferable₂O)/BaO is 0.1 to 3.0, and (CaO + Na) is more preferable₂O)/BaO is 0.2 to 1.0.

In some embodiments of the invention, the content of BaO is adjusted to Na₂O and Nb₂O₅Total content of (Na)₂O+Nb₂O₅) Ratio between BaO/(Na)₂O+Nb₂O₅) Within the range of 0.05-0.8, the hardness of the glass can be improved, and the light transmittance of the glass can be optimized. Therefore, BaO/(Na) is preferable₂O+Nb₂O₅) 0.05 to 0.8, more preferably BaO/(Na)₂O+Nb₂O₅) 0.1 to 0.6, and further preferably BaO/(Na)₂O+Nb₂O₅) 0.15 to 0.5, and further preferably BaO/(Na)₂O+Nb₂O₅) Is 0.2～0.4。

K₂O has the effect of improving the thermal stability and the melting property of the glass, but when K is used₂When the content of O exceeds 8%, the devitrification resistance of the glass is lowered. Thus, K₂The upper limit of the content of O is 8%, preferably 5%, more preferably 4%.

Li₂O、Na₂O、K₂O is an alkali metal oxide, and the inventors have found through extensive experimental studies that, in some embodiments of the present invention, Li is present as Li₂O/(Li₂O+Na₂O+K₂O) is within the range of 0.3-1.0, the devitrification resistance of the glass can be optimized, and the water resistance of the glass is improved. Therefore, Li is preferable₂O/(Li₂O+Na₂O+K₂O) is 0.3 to 1.0, and Li is more preferable₂O/(Li₂O+Na₂O+K₂O) is 0.4 to 0.9. Further, by reacting Li₂O/(Li₂O+Na₂O+K₂O) is within the range of 0.45-0.8, and is also beneficial to improving the weather resistance of the glass. Therefore, Li is more preferable₂O/(Li₂O+Na₂O+K₂O) is 0.45 to 0.8, and Li is more preferable₂O/(Li₂O+Na₂O+K₂O) is 0.5 to 0.75.

La₂O₃Can effectively improve the refractive index of the glass, enhance the chemical stability and the mechanical strength of the glass and simultaneously do not obviously increase the P of the glass_g,FValue sum Δ P_g,FHowever, when the content exceeds 14%, the resistance to devitrification of the glass becomes poor. Thus, La in the glass of the present invention₂O₃The content of (b) is 0 to 14%, preferably 2 to 12%, more preferably 4 to 10%.

As a result of extensive experimental studies by the inventors, it was found that in some embodiments of the present invention, Nb is controlled₂O₅With BaO and La₂O₃Total content of (BaO + La)₂O₃) Ratio between Nb₂O₅/(BaO+La₂O₃) In the range of 0.8 to 8.0, the glass P can be reduced_g,FValue sum Δ P_g,FWhile optimizing the thermal expansion coefficient and the secondary compression resistance of the glassCrystallization performance. Therefore, Nb is preferable₂O₅/(BaO+La₂O₃) 0.8 to 8.0, more preferably Nb₂O₅/(BaO+La₂O₃) 1.0 to 6.0, and more preferably Nb₂O₅/(BaO+La₂O₃) 1.2 to 4.0, and further preferably Nb₂O₅/(BaO+La₂O₃) 1.5 to 3.0.

In some embodiments of the invention, the content of ZnO and BaO and La are controlled₂O₃Total content of (BaO + La)₂O₃) The ratio between ZnO/(BaO + La)₂O₃) When the content is 2.0 or less, the decrease in glass hardness can be prevented. Therefore, ZnO/(BaO + La) is preferable₂O₃) Is 2.0 or less, and ZnO/(BaO + La) is more preferable₂O₃) 0.05 to 1.5. Further, by making ZnO/(BaO + La)₂O₃) In the range of 0.08-1.0, the devitrification resistance and the abrasion degree of the glass can be further optimized, and the thermal expansion coefficient of the glass is prevented from being increased. Therefore, ZnO/(BaO + La) is more preferable₂O₃) 0.08 to 1.0, and further preferably ZnO/(BaO + La)₂O₃) 0.1 to 0.5.

Gd₂O₃Has the effect of increasing the refractive index, but when the content exceeds 10%, the devitrification resistance of the glass decreases and the transition temperature tends to rise, so that Gd in the present invention₂O₃The content of (B) is 10% or less, preferably 0 to 5%, more preferably 0 to 3%.

Y₂O₃The melting property and devitrification resistance of the glass can be improved and the chemical stability of the glass can be improved, but if the content thereof exceeds 10%, the stability and devitrification resistance of the glass are lowered. Thus, Y₂O₃The content of (A) is in the range of 0 to 10%, preferably 0 to 5%, more preferably 0 to 3%, and further preferably Y is not contained₂O₃。

Yb₂O₃The refractive index of the glass can be increased, and if the content exceeds 10%, the stability and devitrification resistance of the glass are lowered. Thus, Yb₂O₃The content of (B) is in the range of 0 to 10%, preferably 0 to 5%,more preferably 0 to 3%, and further preferably does not contain Yb₂O₃。

WO₃Can improve the refractive index and mechanical strength of the glass, if WO₃When the content of (B) exceeds 5%, the thermal stability of the glass is lowered, and the transmittance and the devitrification resistance are lowered. Thus, WO₃The upper limit of the content of (B) is 5%, preferably 3%, more preferably 2%. In some embodiments, it is further preferred that WO is absent₃。

B₂O₃The glass of the invention can be used as a glass network forming body and is beneficial to reducing the P of the glass_g,FValue sum Δ P_g,FThe value is obtained. When B is present₂O₃When the content of (b) is more than 8%, the chemical stability of the glass is deteriorated, the high-temperature viscosity of the glass is decreased, and the transmittance and secondary press type devitrification resistance of the glass are deteriorated. Thus, B₂O₃The content of (b) is limited to 8% or less, preferably 4% or less, and more preferably 2% or less. In some embodiments, it is further preferred not to contain B₂O₃。

In some embodiments of the invention, B is₂O₃/SiO₂The crystallization resistance and the chemical stability of the glass can be improved by controlling the content of the glass to be less than 0.3. Therefore, B is preferred₂O₃/SiO₂Is 0.3 or less, and B is more preferably₂O₃/SiO₂Is 0.2 or less. Further, make B₂O₃/SiO₂Below 0.15, the hardness of the glass is advantageously increased. Therefore, B is more preferable₂O₃/SiO₂Is 0.15 or less, and B is more preferably B₂O₃/SiO₂Is 0.1 or less.

TiO₂Has the function of improving the refractive index and dispersion of the glass, and contains TiO in a proper amount to make the glass more stable and reduce the viscosity of the glass₂The presence of (A) will significantly increase the P of the glass_g,FValue sum Δ P_g,FValue, therefore, TiO in the present invention₂The content of (b) is 5% or less, preferably 3% or less, more preferably 2% or less. In some embodiments, it is further preferred that no TiO is present₂。

Al₂O₃The chemical stability of the glass can be improved, but when the content thereof exceeds 5%, the meltability and light transmittance of the glass are deteriorated. Therefore, Al in the present invention₂O₃The content of (B) is 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%. In some embodiments, it is further preferred that Al is absent₂O₃。

Ta₂O₅Has the advantages of improving the refractive index of the glass and reducing the P of the glass_g,FValue sum Δ P_g,FThe glass has the advantages that the devitrification resistance is improved, but if the content of the glass is too high, the chemical stability of the glass is reduced, the surface tension of the glass is increased, and bubbles are difficult to eliminate; on the other hand, Ta is compared with other components₂O₅The price of (2) is very expensive, and the amount of use should be minimized from the practical and cost viewpoints. Thus, Ta in the present invention₂O₅The content of (A) is limited to 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%, and further preferably no Ta is contained₂O₅。

In the invention, 0-1% of Sb is contained₂O₃、SnO、SnO₂、CeO₂One or more components in the glass can be used as a clarifying agent, so that the clarifying effect of the glass can be improved, and the content of the clarifying agent is preferably 0-0.5%. When Sb is present₂O₃At contents exceeding 1%, the glass tends to have a reduced fining ability, and since the strong oxidizing action promotes the corrosion of the platinum or platinum alloy vessel from which the glass is melted and the deterioration of the forming mold, Sb is preferred in the present invention₂O₃The content of (B) is 0 to 1%, more preferably 0 to 0.5%. SnO and SnO₂However, when the content exceeds 1%, the glass tends to be colored more, or when the glass is heated, softened, press-molded or the like and then reformed, Sn becomes a starting point of crystal nucleus formation, and the glass tends to be devitrified. Thus the SnO of the invention₂The content of (b) is preferably 0 to 1%, more preferably 0 to 0.5%; the content of SnO is preferably 0 to 1%, more preferably 0 to 0.5%. CeO (CeO)₂The function and content ratio of (A) and (B) of SnO₂The content is preferably 0 to 1%, more preferably 0 to 0.5%, and further preferably not containingWith CeO₂。

< component which should not be contained >

In the glass of the present invention, even when a small amount of oxides of transition metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo is contained singly or in combination, the glass is colored and absorbs at a specific wavelength in the visible light region, thereby impairing the property of the present invention to improve the effect of visible light transmittance.

In recent years, oxides of Th, Cd, Tl, Os, Be, and Se tend to Be used as harmful chemical substances in a controlled manner, and measures for protecting the environment 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 influence on the environment, it is preferable that these components are not substantially contained except for inevitable mixing. Thereby, the optical glass becomes practically free from substances contaminating the environment. Therefore, the optical glass of the present invention can be manufactured, processed, and discarded without taking special measures for environmental countermeasures.

In order to achieve environmental friendliness, the optical glass of the present invention preferably does not contain As₂O₃And PbO.

"0%" or "0%" is not contained in the present invention, and means that the compound, molecule, element or the like is not intentionally added to the optical glass of the present invention as a raw material; 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 performance of the optical glass of the present invention will be described below.

< refractive index and Abbe number >

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

In some embodiments, the folding of the optical glass of the present inventionRefractive index (n)_d) The lower limit of (b) is 1.69, preferably 1.71, more preferably 1.72, and still more preferably 1.73. In some embodiments, the refractive index (n) of the optical glass of the present invention_d) The upper limit of (b) is 1.82, preferably 1.80, more preferably 1.77, and still more preferably 1.76.

In some embodiments, the Abbe number (v) of the optical glass of the present invention_d) The lower limit of (2) is 32, the lower limit is preferably 33, and the lower limit is more preferably 34. In some embodiments, the Abbe number (v) of the optical glass of the present invention_d) The upper limit of (2) is 40, preferably 38, and more preferably 37.

< Density >

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

In some embodiments, the optical glass of the present invention has a density (. rho.) of 3.80g/cm³Hereinafter, it is preferably 3.70g/cm³Hereinafter, more preferably 3.60g/cm³The following.

< coefficient of thermal expansion >

Coefficient of thermal expansion (alpha) of optical glass_-30/70℃) And testing data at-30-70 ℃ according to a method specified in GB/T7962.16-2010.

In some embodiments, the optical glass of the present invention has a coefficient of thermal expansion (α)_-30/70℃) Is 95X 10^-7Preferably 90X 10 or less,/K^-7A value of not more than 85X 10^-7and/K is less than or equal to.

< transition temperature >

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

In some embodiments, the transition temperature (T) of the optical glass of the present invention_g) Is 600 ℃ or lower, preferably 590 ℃ or lower, and more preferably 580 ℃ or lower.

< degree of coloration >

Coloring degree (. lamda.) for short-wave transmission spectral characteristics of the glass of the present invention₈₀And λ₅) And (4) showing. Lambda [ alpha ]₈₀Means that the transmittance of the glass reaches 80 percentThe corresponding wavelength. Lambda [ alpha ]₈₀Was measured using a glass having a thickness of 10. + -. 0.1mm with two opposing planes parallel to each other and optically polished, measuring the spectral transmittance in the wavelength region from 280nm to 700nm and showing a wavelength of transmittance of 80%. The spectral transmittance or transmittance is the intensity I of light incident perpendicularly to the surface of the glass_inLight transmitted through the glass and having an intensity I emitted from a plane_outIn the case of light of (1) through (I)_out/I_inThe quantity expressed and also the transmission of the surface reflection losses on the above-mentioned surface of the glass. The higher the refractive index of the glass, the greater the surface reflection loss. Thus, in high refractive index glasses, λ₈₀A small value of (A) means that the glass itself is rarely colored and has a high light transmittance.

In some embodiments, the λ of the optical glass of the present invention₈₀Less than or equal to 410nm, preferably lambda₈₀Less than or equal to 400nm, more preferably lambda₈₀Less than or equal to 395 nm.

In some embodiments, the λ of the optical glass of the present invention₅Less than or equal to 340nm, preferably lambda₅Less than or equal to 335nm, more preferably lambda₅Less than or equal to 330 nm.

< stability against Water action >

Stability to Water of optical glass (D)_W) (powder method) the test was carried out according to the method prescribed in GB/T17129.

In some embodiments, the optical glass of the present invention has stability to water effects (D)_W) Is 2 or more, preferably 1.

< stability against acid Effect >

Stability of acid resistance of optical glasses (D)_A) (powder method) the test was carried out according to the method prescribed in GB/T17129.

In some embodiments, the stability to acid action of the optical glasses of the invention (D)_A) Is 2 or more, preferably 1.

< Knoop hardness >

Knoop hardness (H) of optical glass_K) Testing according to GB/T7962.18-2010The method was tested.

In some embodiments, the Knoop hardness (H) of the optical glasses of the present invention_K) Is 530 x 10⁷Pa or more, preferably 550X 10⁷Pa or more, more preferably 570X 10⁷Pa or above.

< relative partial dispersion and relative partial dispersion deviation value >

The relative partial dispersion (P) is illustrated by the following equation_g,F) And relative partial dispersion deviation value (Δ P)_g,F) The origin of (1).

The relative partial dispersion for wavelengths x and y is represented by the following formula (1):

P_x,y＝(n_x-n_y)/(n_F-n_C) (1)

the following formula (2) holds for most of the so-called "normal glasses" according to the Abbe number formula (hereinafter, H-K6 and F4 are used as "normal glasses")

P_x,y＝m_x,y·v_d+b_x,y (2)

This linear relationship is P_x,yIs ordinate, v_dExpressed on the abscissa, where m_x,yIs a slope, b_x,yIs the intercept.

It is known that the correction of the secondary spectrum, i.e. the achromatization of more than two wavelengths, requires at least one glass which does not conform to the above formula (2) (i.e. its P)_x,yValue deviation from Abbe's empirical formula) by Δ P_x,yIndicates that each P is_x,y-v_dThe point being shifted by Δ P with respect to a "normal line" corresponding to the above formula (2)_x,yAmount of such a.DELTA.P of each glass_x,yThe numerical value can be obtained by the following formula (3):

P_x,y＝m_x,y·v_d+b_x,y+ΔP_x,y (3)

thus Δ P_x,yQuantitatively indicating the deviation behavior of the specific dispersion when compared to "normal glass".

Therefore, from the above, relative partial dispersion (P) can be obtained_g,F) And relative partial dispersion deviation value (Δ P)_g,F) Is calculated by the formulaThe following formulae (4) and (5):

P_g,F＝(n_g-n_F)/(n_F-n_C) (4)

ΔP_g,F＝P_g,F-0.6457+0.001703v_d (5)

in some embodiments, the relative partial dispersion (P) of the optical glasses of the present invention_g,F) Is 0.7000 or less, preferably 0.6500 or less, and more preferably 0.6000 or less.

In some embodiments, the optical glasses of the present invention have a relative partial dispersion deviation value (Δ P)_g,F) Less than 0, preferably not more than-0.0010, more preferably not more than-0.0020, and still more preferably not more than-0.0030.

< resistance to devitrification >

The method for testing the anti-devitrification performance comprises the following steps: cutting the sample glass into a size of 20 × 20 × 10mm, and placing at a temperature T_gAnd (4) preserving the heat in a muffle furnace at 200-250 ℃ for 15-30 minutes, taking out and cooling, and observing whether crystals exist on the surface and the inside of the glass or opacification occurs. If the glass sample is free from opalescence and crystals, the devitrification resistance of the glass is excellent. The test method is used for representing the secondary compression anti-devitrification performance of the glass.

[ method for producing optical glass ]

The method for manufacturing the optical glass comprises the following steps: the glass is produced by adopting conventional raw materials and processes, including but not limited to oxides, hydroxides, carbonates, nitrates, phosphates, metaphosphates and the like as raw materials, after the materials are mixed by a conventional method, the mixed furnace materials are put into a smelting furnace (such as a platinum or platinum alloy crucible) at 1200-1400 ℃ for smelting, and after clarification and homogenization, homogeneous molten glass without bubbles and undissolved substances is obtained, and the molten glass is cast in a mould and annealed. Those skilled in the art can appropriately select the raw materials, the process method and the process parameters according to the actual needs.

Glass preform and optical element

The glass preform can be produced from the optical glass produced by direct gob casting, grinding, or press molding such as hot press molding. That is, a glass preform can be produced by direct precision gob-molding of molten optical glass into a glass precision preform, or by mechanical processing such as grinding and polishing, or by producing a preform for press molding from optical glass, subjecting the preform to reheat press molding, and then performing polishing processing. It should be noted that the means for producing 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 among them, it is particularly preferable to form a preform from the optical glass of the present invention, and use the preform for reheat press forming, precision press forming, or the like to produce optical elements such as lenses, prisms, or the like.

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

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.

[ optical instruments ]

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

Examples

< example of optical glass >

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

In this example, optical glasses having compositions shown in tables 1 to 5 were obtained by the above-mentioned method for producing optical glasses. The characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in tables 1 to 5. In the test of devitrification resistance in tables 1 to 5, according to the above test method, the glass is opaque and has no crystal particles inside it as "A", no opaque and 1 to 10 crystal particles inside it as "B", no opaque and 10 to 20 crystal particles inside it as "C", and the glass is opaque or has densely crystallized particles inside it as "X".

Table 1.

Table 2.

Table 3.

Table 4.

Table 5.

< glass preform example >

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 preforms such as prisms were produced by using the glasses obtained in examples 1 to 32 of optical glass by means of polishing or press molding such as reheat press molding and precision press molding.

< optical element example >

The preforms obtained from the above glass preform examples were annealed to reduce the internal stress of the glass and to fine-tune the refractive index so that the optical properties such as refractive index reached the 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 resulting optical element may be coated with an antireflection film.

< optical Instrument example >

The optical element produced by the above-described optical element embodiments can be used, for example, for imaging devices, sensors, microscopes, medical technology, digital projection, communication, optical communication technology/information transmission, optics/illumination in the automotive field, lithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, by optical design, by forming an optical component or optical assembly using one or more optical elements.

Claims

1. Optical glass, characterized in that its components, expressed in weight percent, contain: SiO 2₂：23～45％；Nb₂O₅：20～40％；ZrO₂：2～14％；BaO：2～18％；Li₂O：1～12％；La₂O₃: 0 to 14% of Nb₂O₅/(BaO+La₂O₃) Is 0.8 to 8.0.

2. An optical glass according to claim 1, characterised in that it further comprises, in percentages by weight: ZnO: 0 to 10 percent; and/or CaO: 0 to 18 percent; and/or SrO: 0-8%; and/or MgO: 0-8%; and/or Na₂O: 0 to 10 percent; and/or K₂O: 0-8%; and/or Gd₂O₃: 0 to 10 percent; and/or Y₂O₃: 0 to 10 percent; and/or Yb₂O₃: 0 to 10 percent; and/or WO₃: 0 to 5 percent; and/or B₂O₃: 0-8%; and/or TiO₂: 0 to 5 percent; and/or Al₂O₃: 0 to 5 percent; and/or Ta₂O₅: 0 to 5 percent; and/or a clarifying agent: 0-1% of a clarifying agent Sb₂O₃、SnO、SnO₂、CeO₂One or more of (a).

3. Optical glass, characterized in that its composition, expressed in weight percentage, is represented by SiO₂：23～45％；Nb₂O₅：20～40％；ZrO₂：2～14％；BaO：2～18％；Li₂O：1～12％；La₂O₃：0～14％；ZnO：0～10％；CaO：0～18％；SrO：0～8％；MgO：0～8％；Na₂O：0～10％；K₂O：0～8％；Gd₂O₃：0～10％；Y₂O₃：0～10％；Yb₂O₃：0～10％；WO₃：0～5％；B₂O₃：0～8％；TiO₂：0～5％；Al₂O₃：0～5％；Ta₂O₅: 0 to 5 percent; a clarifying agent: 0 to 1% of Nb₂O₅/(BaO+La₂O₃) 0.8-8.0, and the clarifying agent is Sb₂O₃、SnO、SnO₂、CeO₂One or more of (a).

4. An optical glass according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: nb₂O₅/(BaO+La₂O₃) 1.0 to 6.0; and/or ZnO/(BaO + La)₂O₃) Is 2.0 or less; and/or (CaO + Na)₂O)/BaO is 0.02-8.0; and/or BaO/(Na)₂O+Nb₂O₅) 0.05 to 0.8; and/or SiO₂/Nb₂O₅0.65 to 2.0; and/or Li₂O/(Li₂O+Na₂O+K₂O) is 0.3 to 1.0; and/or SiO₂V (BaO + ZnO) is 1.0-20.0; and/or B₂O₃/SiO₂Is 0.3 or less.

5. An optical glass according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: nb₂O₅/(BaO+La₂O₃) 1.2 to 4.0; and/or ZnO/(BaO + La)₂O₃) 0.05 to 1.5; and/or (CaO + Na)₂O)/BaO is 0.05 to 5.0; and/or BaO/(Na)₂O+Nb₂O₅) 0.1 to 0.6; and/or SiO₂/Nb₂O₅0.75 to 1.8; and/or Li₂O/(Li₂O+Na₂O+K₂O) is 0.4 to 0.9; and/or SiO₂V (BaO + ZnO) is 1.5-15.0; and/or B₂O₃/SiO₂Is 0.2 or less.

6. An optical glass according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: nb₂O₅/(BaO+La₂O₃) 1.5 to 3.0; and/or ZnO/(BaO + La)₂O₃) 0.08 to 1.0; and/or (CaO + Na)₂O)/BaO is 0.1 to 3.0; and/or BaO/(Na)₂O+Nb₂O₅) 0.15 to 0.5; and/or SiO₂/Nb₂O₅0.8 to 1.5; and/or Li₂O/(Li₂O+Na₂O+K₂O) is 0.45 to 0.8; and/or SiO₂V (BaO + ZnO) is 2.0-10.0; and/or B₂O₃/SiO₂Is 0.15 or less.

7. An optical glass according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: ZnO/(BaO + La)₂O₃) 0.1 to 0.5; and/or (CaO + Na)₂O)/BaO is 0.2 to 1.0; and/or BaO/(Na)₂O+Nb₂O₅) 0.2 to 0.4; and/or SiO₂/Nb₂O₅0.9 to 1.3; and/or Li₂O/(Li₂O+Na₂O+K₂O) is 0.5 to 0.75; and/or SiO₂V (BaO + ZnO) is 2.5-5.0; and/or B₂O₃/SiO₂Is 0.1 or less.

8. An optical glass according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: SiO 2₂: 28-42%, preferably SiO₂: 31-40%; and/or Nb₂O₅: 22 to 37%, preferably Nb₂O₅: 26 to 33 percent; and/or ZrO₂: 3 to 12%, preferably ZrO₂: 5-10%; and/or BaO: 4-15%, preferably BaO: 5-12%; and/or Li₂O: 1 to 10%, preferably Li₂O: 1-9%; and/or La₂O₃: 2-12%, preferably La₂O₃: 4-10%; and/or ZnO: 0.1-8%, preferably ZnO: 0.5-6%; and/or CaO: 0-16.5%, preferably CaO: 0-8%; and/or SrO: 0 to 5%, preferably SrO: 0-2%; and/or MgO: 0-5%, preferably MgO: 0-2%; and/or Na₂O: 0.5-8%, preferably Na₂O: 1-6%; and/or K₂O: 0 to 5%, preferably K₂O：0 to 4 percent; and/or Gd₂O₃: 0 to 5%, preferably Gd₂O₃: 0 to 3 percent; and/or Y₂O₃: 0 to 5%, preferably Y₂O₃: 0 to 3 percent; and/or Yb₂O₃: 0 to 5%, preferably Yb₂O₃: 0 to 3 percent; and/or WO₃: 0 to 3%, preferably WO₃: 0-2%; and/or B₂O₃: 0 to 4%, preferably B₂O₃: 0-2%; and/or TiO₂: 0 to 3%, preferably TiO₂: 0-2%; and/or Al₂O₃: 0 to 2%, preferably Al₂O₃: 0 to 1 percent; and/or Ta₂O₅: 0 to 2%, preferably Ta₂O₅: 0 to 1 percent; and/or a clarifying agent: 0-0.5%, the clarifying agent is Sb₂O₃、SnO、SnO₂、CeO₂One or more of (a).

9. An optical glass according to any one of claims 1 to 3, wherein the component does not contain B₂O₃(ii) a And/or does not contain TiO₂(ii) a And/or does not contain WO₃(ii) a And/or does not contain Ta₂O₅(ii) a And/or does not contain SrO; and/or does not contain MgO; and/or does not contain CaO; and/or does not contain Gd₂O₃(ii) a And/or does not contain Y₂O₃。

10. An optical glass according to any one of claims 1 to 3, wherein the refractive index n of the optical glass_d1.69 to 1.82, preferably 1.71 to 1.80, more preferably 1.72 to 1.77, still more preferably 1.73 to 1.76, and/or Abbe number v_dIs 32 to 40, preferably 33 to 38, and more preferably 34 to 37.

11. An optical glass according to any one of claims 1 to 3, wherein the relative partial dispersion P of the optical glass_g,FIs 0.7000 or less, preferably 0.6500 or less, more preferably 0.6000 or less, and/or a relative partial dispersion deviation value Δ P_g,FLess than 0, preferably not more than-0.0010, more preferably not more than-0.0020, and still more preferably not more than-0.0030.

12. The optical glass according to any one of claims 1 to 3, wherein the density p of the optical glass is 3.80g/cm³Hereinafter, it is preferably 3.70g/cm³Hereinafter, more preferably 3.60g/cm³The following; and/or coefficient of thermal expansion alpha_-30/70℃Is 95X 10^-7Preferably 90X 10 or less,/K^-7A value of not more than 85X 10^-7below/K; and/or transition temperature T_g600 ℃ or lower, preferably 590 ℃ or lower, more preferably 580 ℃ or lower; and/or lambda₈₀Less than or equal to 410nm, preferably lambda₈₀Less than or equal to 400nm, more preferably lambda₈₀Less than or equal to 395 nm; and/or lambda₅Less than or equal to 340nm, preferably lambda₅Less than or equal to 335nm, more preferably lambda₅Less than or equal to 330 nm; 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 Knoop hardness H_KIs 530 x 10⁷Pa or more, preferably 550X 10⁷Pa or more, more preferably 570X 10⁷Pa or above.

13. A glass preform characterized by being made of the optical glass according to any one of claims 1 to 12.

14. An optical element produced from the optical glass according to any one of claims 1 to 12 or the glass preform according to claim 13.

15. An optical device comprising the optical glass according to any one of claims 1 to 12 and/or comprising the optical element according to claim 14.