CN109626814B

CN109626814B - Environment-friendly optical glass, optical prefabricated member, optical element and optical instrument

Info

Publication number: CN109626814B
Application number: CN201910012401.1A
Authority: CN
Inventors: 袁伟; 赖德光
Original assignee: CDGM Glass Co Ltd
Current assignee: CDGM Glass Co Ltd
Priority date: 2019-01-07
Filing date: 2019-01-07
Publication date: 2021-09-28
Anticipated expiration: 2039-01-07
Also published as: CN109626814A

Abstract

The invention provides environment-friendly optical glass, which comprises the following components in percentage by weight: SiO 2₂：30～50％、TiO₂：2～20％、ZnO：15～35％、ZrO₂：0～10％、BaO：5～24％、Na₂O：0～15％、K₂O: 0 to 10%, wherein the ZnO/BaO is 0.8 to 5.0. Through reasonable component design, the optical material has excellent chemical stability under the condition of obtaining optical properties such as expected refractive index and Abbe number.

Description

Environment-friendly optical glass, optical prefabricated member, optical element and optical instrument

Technical Field

The invention relates to optical glass, in particular to environment-friendly optical glass, an optical prefabricated member, an optical element and an optical instrument.

Background

With the continuous fusion of optics and electronic information science and new material science, the application of optical glass as a photoelectron base material in the technical fields of light transmission, light storage, photoelectric display and the like is rapidly advanced. In recent years, optical elements and optical instruments have been rapidly developed in terms of digitization, integration, and high definition, which has made higher demands on the performance of optical glasses used in optical elements of optical instruments and devices.

The optical glass is likely to be corroded by the environment and various chemical reagents and liquid medicines during the use process, so the resistance of the optical glass to the corrosion, namely the chemical stability of the optical glass is very important for the use precision and the service life of the instrument. Meanwhile, with the increasing call for environmental protection in the world, research and development work for lead-free and arsenic-free optical glass is continuously ongoing, for example, the optical glass disclosed in CN101549955A contains 20-60% of lead oxide, which obviously does not meet the requirement of environmental protection.

Disclosure of Invention

For the above reasons, the technical problem to be solved by the present invention is to provide an environmentally friendly optical glass having excellent chemical stability, and an optical preform, an optical element and an optical instrument.

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

(1) the environment-friendly optical glass comprises the following components in percentage by weight: SiO 2₂：30～50％、TiO₂：2～20％、ZnO：15～35％、ZrO₂：0～10％、BaO：5～24％、Na₂O：0～15％、K₂O: 0 to 10%, wherein the ZnO/BaO is 0.8 to 5.0.

(2) The environment-friendly optical glass comprises the following components in percentage by weight: SiO 2₂：30～50％、TiO₂：2～20％、ZnO：15～35％、ZrO₂：0～10％、BaO：5～24％、Na₂O：0～15％、K₂O：0～10％。

(3) The environment-friendly optical glass according to any one of (1) and (2), which further comprises the following components in percentage by weight: li₂O：0～10％、Nb₂O₅：0～8％、Ln₂O₃：0～10％、B₂O₃：0～10％、CaO：0～8％、SrO：0～8％、MgO：0～8％、Al₂O₃：0～8％、WO₃: 0-8% of a clarifying agent: 0 to 1% of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂SnO and CeO₂One or more of (a).

(4) The environment-friendly optical glass comprises the components expressed by weight percentage and is made of SiO₂：30～50％、TiO₂：2～20％、ZnO：15～35％、ZrO₂：0～10％、BaO：5～24％、Na₂O：0～15％、K₂O：0～10％、Li₂O：0～10％、Nb₂O₅：0～8％、Ln₂O₃：0～10％、B₂O₃：0～10％、CaO：0～8％、SrO：0～8％、MgO：0～8％、Al₂O₃：0～8％、WO₃: 0-8% of a clarifying agent: 0 to 1%, wherein ZnO/BaO is 0.8 to 5.0, Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂SnO and CeO₂One or more of (a).

(5) Environmental protection optical glass containing SiO₂、TiO₂ZnO, alkali metal oxide and alkaline earth metal oxide, wherein the refractive index (nd) of the environment-friendly optical glass is 1.64-1.71, and the Abbe number (v)_d) 35-40, the upper limit temperature of crystallization is less than 1150 ℃, and the alkali metal oxide is Na₂O、K₂O and Li₂One or more of O, and the alkaline earth metal oxide is one or more of MgO, CaO, SrO and BaO.

(6) The eco-friendly optical glass according to any one of (1) to (5), wherein: SiO 2₂: 35 to 50%, and/or TiO₂: 5-15%, and/or ZnO: 18 to 30%, and/or ZrO₂: 0.5-8%, and/or BaO: 8 to 22%, and/or Na₂O: 3 to 12%, and/or K₂O: 0.5 to 8%, and/or Li₂O: 0 to 5%, and/or Nb₂O₅: 0 to 5%, and/or Ln₂O₃: 0 to 5%, and/or B₂O₃: 0-5%, and/or CaO: 0-5%, and/or SrO: 0-5%, and/or MgO: 0 to 5%, and/or Al₂O₃: 0 to 5%, and/or WO₃: 0-5%, and/or a clarifying agent: 0 to 0.5%, wherein Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂SnO and CeO₂One or more of (a).

(7) The eco-friendly optical glass according to any one of (1) to (6), wherein: SiO 2₂: 35 to 45%, and/or TiO₂: 7-13%, and/or ZnO: 20 to 28%, and/or ZrO₂: 1-5%, and/or BaO: 10 to 18%, and/or Na₂O: 5 to 10%, and/or K₂O: 1 to 5%, and/or Li₂O: 0 to 2%, and/or Nb₂O₅: 0 to 2%, and/or Ln₂O₃: 0 to 3%, and/or B₂O₃: 0-2%, and/or CaO: 0-2%, and/or SrO: 0-2%, and/or MgO: 0 to 2%, and/or Al₂O₃: 0 to 2%, and/or WO₃: 0 to 3%, and/or Sb₂O₃: 0 to 0.5%, wherein Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃One or more of (a).

(8) The eco-friendly optical glass according to any one of (1) to (7), wherein: the ZnO/BaO is 1.0 to 3.0, preferably 1.2 to 2.5.

(9) The eco-friendly optical glass according to any one of (1) to (8), wherein: TiO 2₂/SiO₂0.15 to 0.5, preferably TiO₂/SiO₂0.15 to 0.4, preferably TiO₂/SiO₂0.2 to 0.35.

(10) The eco-friendly optical glass according to any one of (1) to (9), wherein: nb₂O₅The value of/ZnO is 0.4 or less, preferably Nb₂O₅The value of/ZnO is 0.2 or less, and Nb is more preferable₂O₅The value of/ZnO is 0.1 or less.

(11) The eco-friendly optical glass according to any one of (1) to (10), wherein: k₂O/(Li₂O+Na₂O+K₂O) has a value of 0.1 to 0.45, preferably K₂O/(Li₂O+Na₂O+K₂O) is 0.12 to 0.4, more preferably K₂O/(Li₂O+Na₂O+K₂O) is 0.15 to 0.35.

(12) The eco-friendly optical glass according to any one of (1) to (11), wherein: (Na)₂O+K₂O)/BaO is 0.2 to 2.0, preferably (Na)₂O+K₂O)/BaO is 0.3 to 1.5, and (Na) is more preferable₂O+K₂O)/BaO is 0.4 to 1.0.

(13) The eco-friendly optical glass according to any one of (1) to (12), wherein: (SiO)₂+ZrO₂)/(ZnO+TiO₂) 0.55 to 3.0, preferably (SiO)₂+ZrO₂)/(ZnO+TiO₂) In the range of 0.7 to 2.5, more preferably (SiO)₂+ZrO₂)/(ZnO+TiO₂) 0.8 to 1.8.

(14) The eco-friendly optical glass according to any one of (1) to (13), wherein: BaO/(MgO + CaO + SrO + BaO) is 0.7 to 1.0, preferably BaO/(MgO + CaO + SrO + BaO) is 0.8 to 1.0, and more preferably BaO/(MgO + CaO + SrO + BaO) is 0.9 to 1.0.

(15) The eco-friendly optical glass according to any one of (1) to (14), wherein: (Li)₂O+ZnO)/SiO₂0.35 to 1.2, preferably (Li)₂O+ZnO)/SiO₂0.4 to 1.0, more preferably (Li)₂O+ZnO)/SiO₂0.45 to 0.85.

(16) The eco-friendly optical glass according to any one of (1) to (15), wherein a refractive index (nd) of the eco-friendly optical glass is 1.64 to 1.71, preferably 1.65 to 1.70, and more preferably 1.66 to 1.69; abbe number (v)_d) 35 to 40, preferably 36 to 40, and more preferably 36 to 39.

(17) The eco-friendly optical glass according to any one of (1) to (16), wherein the eco-friendly optical glass has a water-resistant stability (D)_W) Is 2 or more, preferably 1; and/or stability against acid action (D)_A) Is 2 or more, preferably 1.

(18) The eco-friendly optical glass according to any one of (1) to (17), wherein the degree of foaming of the eco-friendly optical glass is class B or more, preferably class A or more, and more preferably class A₀More than grade; and/or the degree of streaking is at least level C, preferably at least level B.

(19) The eco-friendly optical glass according to any one of (1) to (18), wherein the coefficient of thermal expansion (α) of the eco-friendly optical glass_20～120℃) Is 85X 10^-7Preferably 80X 10 or less,/K^-7A value of 78X 10 or less, more preferably^-7below/K; and/or the upper crystallization temperature is 1150 ℃ or lower, preferably 1100 ℃ or lower, and more preferably 1050 ℃ or lower; and/or transition temperatureDegree (T)_g) Is 600 ℃ or lower, preferably 590 ℃ or lower, more preferably 585 ℃.

(20) The optical prefabricated member is made of the environment-friendly optical glass in any one of (1) to (19).

(21) An optical element made of the environmentally friendly optical glass of any one of (1) to (19), or the optical preform of claim 20.

(22) An optical device comprising the eco-friendly optical glass according to any one of (1) to (19) or comprising the optical element according to claim 21.

The invention has the beneficial effects that: the invention has excellent chemical stability under the condition of obtaining optical properties such as expected refractive index, Abbe number and the like through reasonable component design.

Detailed Description

The present invention is not limited to the embodiments described below, and can be carried out with appropriate modifications within the scope of the object of the present invention. Note that, although the description of the duplicate description may be appropriately omitted, the gist of the invention is not limited to this. Hereinafter, the "eco-friendly optical glass" of the present invention is sometimes referred to simply as optical glass or glass.

[ optical glass ]

The ranges of the respective components of the optical glass of the present invention are explained below. In the present specification, the contents of the respective components are all expressed in terms of weight percentage with respect to the total amount of glass matter 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%.

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.

< essential Components and optional Components >

SiO₂Is an essential component of the optical glass of the present invention, and is a skeleton of the optical glass of the present invention. By mixing SiO₂The content of (3) is designed to be more than 30%, so that the acid resistance and viscosity of the glass can be improved, and the abrasion degree of the glass can be reduced. Thus, SiO in the present invention₂The lower limit of the content of (B) is 30%, and the preferable lower limit is 35%. But when SiO₂When the content of (b) exceeds 50%, the melting property of the glass is drastically deteriorated, and the coloring of the glass is likely to increase. Thus, SiO in the present invention₂The upper limit of the content of (B) is 50%, preferably 45%.

TiO₂Has the performance of high refraction and high dispersion, and can improve the refractive index of the glass when being added into the optical glass. In the invention, more than 2 percent of TiO is introduced₂The devitrification resistance and chemical stability of the glass can be improved. Thus, TiO in the optical glass of the present invention₂The lower limit of (2) is preferably 5%, more preferably 7%. On the other hand, by controlling TiO₂When the content is less than 20%, the coloring of the glass can be reduced, and the transmittance of the glass at a short wavelength can be improved. In some embodiments, by controlling TiO₂At most 15%, the partial dispersion ratio of the glass is not easily increased, and a glass having a low partial dispersion ratio can be easily obtained. Therefore, TiO in the optical glass of the present invention₂The upper limit of (2) is 20%, preferably 15%, more preferably 13%.

In some embodiments of the invention, the TiO is controlled₂And SiO₂Content ratio of TiO₂/SiO₂The range of (A) is 0.15 to 0.5, the devitrification resistance of the glass can be improved, desired optical constants and chemical stability can be easily obtained, and further, TiO is preferably used₂/SiO₂The range of (3) is 0.15 to 0.4, and contributes to improvement of meltability of glass and light transmittance of glass, and TiO is more preferable₂/SiO₂The range of (A) is 0.2 to 0.35.

ZrO₂The glass belongs to high-refractive-index oxides, and can improve the refractive index of the glass and the chemical stability of the glass; in the present invention, by containing 10% or less of ZrO₂And also has the effect of improving the abnormal dispersibility of the glass, which is favorable for eliminating secondary spectrum in optical design, so that ZrO in the optical glass of the present invention₂The content of (B) is 10% or less. In some embodiments, ZrO₂The content of (b) is less than 0.5%, the above effects are not significant, but the addition amount thereof exceeds 8%, the risk of devitrification of the glass is increased. Thus, ZrO₂The content of (b) is preferably 0.5 to 8%, more preferably 1 to 5%.

Nb₂O₅Is a high-refraction high-dispersion component, is an optional component in the invention, and controls Nb₂O₅When the content of (b) is 8% or less, the glass can be inhibited from decreasing in devitrification resistance and can be easily obtained with desired dispersion. Therefore, Nb in the optical glass of the present invention₂O₅The content of (b) is 8% or less, preferably 5% or less, more preferably 2% or less. In some embodiments, by not containing Nb₂O₅The transmittance and anti-devitrification performance of the glass can be improved.

ZnO is an essential component for lowering the glass transition temperature and the melting temperature of the glass raw material in the present invention. By containing more than 15% of ZnO, the chemical stability of the glass can be improved, the meltability of raw materials can be improved, the discharge of glass bubbles can be promoted, and the high-temperature viscosity of the glass can be reduced; however, when the ZnO content is more than 35%, the devitrification resistance of the glass is deteriorated and devitrification is liable to occur due to too low viscosity. Therefore, the content of ZnO in the optical glass is 15-35%, preferably 18-30%, and more preferably 20-28%.

In some embodiments of the invention, Nb is controlled₂O₅The value of/ZnO is less than 0.4, the viscosity of the glass can be improved, and the optical glass can obtain excellent bubble degree, especially Nb₂O₅The value of/ZnO is 0.2 or less, the chemical stability of the optical glass can be improved, and the bubble degree of the optical glass can be made to be A grade or more, more preferably Nb₂O₅The value of/ZnO is 0.1 or less.

The inventors have discovered, through research, that in some embodiments of the present invention, the chemical composition is prepared by reacting (SiO)₂+ZrO₂)/(ZnO+TiO₂) Within the range of 0.55-3.0, the optical glass can obtain excellent chemical stability and glass forming stability; further reacting (SiO)₂+ZrO₂)/(ZnO+TiO₂) In the range of 0.7 to 2.5, the bubble degree of the optical glass can be optimized, and (SiO) is more preferable₂+ZrO₂)/(ZnO+TiO₂) 0.8 to 1.8.

BaO improves the devitrification resistance of the glass and adjusts the thermal expansion coefficient of the glass. In particular, in the present invention, desired optical constants and chemical stability can be obtained for the optical glass of the present invention by introducing BaO of 5% or more, and therefore, the lower limit of the content of BaO is 5%, preferably 8%, more preferably 10%. On the other hand, when the BaO content is 24% or less, the light transmittance of the glass can be improved and the glass in the molten state can be stabilized. Therefore, the upper limit of the content of BaO is 24%, preferably 22%, more preferably 18%.

Through a great deal of experimental research of the inventor, the optical glass can obtain excellent chemical stability by enabling the range of ZnO/BaO to be 0.8-5.0; further, when the value of ZnO/BaO exceeds 3.0, the devitrification resistance of the glass is lowered, and when the value of ZnO/BaO is less than 1.0, the transition temperature and the thermal expansion coefficient of the glass are raised, so that in some embodiments of the optical glass of the present invention, it is preferable that the range of ZnO/BaO is 1.0 to 3.0; furthermore, the optical glass of the invention can obtain excellent striation by controlling the range of ZnO/BaO to be 1.2-2.5.

CaO is a component that increases the devitrification resistance and reduces the degree of glass abrasion, and is an optional component in the glass of the present invention. In the present invention, by setting the CaO content to 8% or less, the devitrification resistance of the glass can be improved and the decrease in the refractive index of the glass can be suppressed. Therefore, in the present invention, the upper limit of the content of CaO is 8%, preferably 5%, and more preferably 2%.

SrO is effective for adjusting the optical constants of the glass, but if the content is too large, the devitrification resistance of the glass is lowered. In the present invention, the upper limit of the content of SrO is controlled to 8%, preferably 5%, and more preferably 2%.

MgO can adjust the optical constants of the glass and improve the chemical stability of the glass, and is an optional component of the optical glass. In the present invention, the meltability of the glass can be improved by containing not more than 8% of MgO. Therefore, in the present invention, the upper limit of the MgO content is 8%, preferably 5%, and more preferably 2%.

MgO, CaO, SrO and BaO are all alkaline earth metal oxides, but the roles in the optical glass of the present invention are different and therefore they are not freely replaceable with each other. Through a great deal of experimental research of the inventor, the content proportion of MgO, CaO, SrO and BaO in a glass system has important influence on the performance of the optical glass; further, when the range of BaO/(MgO + CaO + SrO + BaO) is 0.7 to 1.0, the optical glass can have excellent thermal expansion coefficient and striae, and the range of BaO/(MgO + CaO + SrO + BaO) is preferably 0.8 to 1.0, and the range of BaO/(MgO + CaO + SrO + BaO) is more preferably 0.9 to 1.0.

Na₂O is a component for improving the meltability of the glass. In the present invention, Na is added₂The content of O is 15% or less, and the chemical stability of the glass is improved and the thermal expansion coefficient of the glass is reduced. In some embodiments, it is preferred to react Na₂The content of O is within the range of 3-12%, the formability of the glass is optimized, and the light transmittance is improved. Therefore, in the optical glass of the present invention, Na₂The O content is limited to 15% or less, preferably 3 to 12%, more preferably 5 to 10%.

K₂O can lower the glass transition temperature, but if the content is more than 10%, the glass is lowered in devitrification resistance. In some embodiments, 0.5-8% of K is preferably introduced₂O, the glass can obtain excellent water-resistant action stability. Thus, in the present invention K₂The O content is limited to 10% or less, preferably 0.5 to 8%, more preferably 1 to 5%.

Li₂O lowers the glass transition temperature, but if it is more than 10%, the glass is lowered in the stability against acid action, and therefore, Li in the present invention₂The content of O is controlled below 10%. In some embodiments, by controlling Li₂The content of O is less than 5%, so that the viscosity of the glass can be improved, and the striae degree of the glass can be improved. Thus, Li₂The content of O is preferably 5% or less, more preferably 2% or less.

Although Li₂O、Na₂O and K₂O is an alkali metal oxide, but the roles in the optical glass of the present invention are different, and the properties of the optical glass can be further optimized by adjusting the contents thereof in the optical glass, respectively. In some embodiments of the invention, K is selected from the group consisting of₂O/(Li₂O+Na₂O+K₂O) is in the range of 0.1 to 0.45, the devitrification resistance of the optical glass can be improved, and especially the K is increased₂O/(Li₂O+Na₂O+K₂O) value is in the range of 0.12 to 0.4, and the degree of striae of the glass can be improved, and K is more preferable₂O/(Li₂O+Na₂O+K₂O) is 0.15 to 0.35. In some embodiments, by reacting Na₂O content > Li₂O content, preferably Na₂The content of O is more than K₂O content > Li₂The content of O can improve the anti-crystallization performance and the chemical stability of the optical glass.

In some embodiments, (Li) is₂O+ZnO)/SiO₂When the amount is more than 1.2, the devitrification resistance of the optical glass is lowered, when (Li)₂O+ZnO)/SiO₂When less than 0.35, the transition temperature of the optical glass increases, so that (Li) in the present invention₂O+ZnO)/SiO₂The range of (a) is 0.35 to 1.2; through further research, the (Li) is found to be₂O+ZnO)/SiO₂In the range of 0.4 to 1.0, the optical glass can be made to have an excellent bubble content, and (Li) is more preferable₂O+ZnO)/SiO₂0.45 to 0.85.

In some embodiments, (Na) is₂O+K₂The value of O)/BaO is higher than 2.0, the thermal expansion coefficient of the glass increases, the striae degree decreases, and when (Na)₂O+K₂The value of O)/BaO is less than 0.2, and the density of the glass increases, so that (Na) is preferable for the optical glass of the present invention₂O+K₂O)/BaO has a value of 0.2 to2.0, more preferably 0.3 to 1.5, and still more preferably 0.4 to 1.0.

B₂O₃Has the effect of improving the thermal stability and meltability of the glass, but when the content thereof is more than 10%, the chemical stability and devitrification resistance of the glass are lowered. In the invention B₂O₃The upper limit of (2) is 10%, preferably 5%, more preferably 2%. In some embodiments, by not introducing B₂O₃The desired chemical stability can be obtained.

Al₂O₃The chemical stability of the glass can be improved, but the content is too large, and the devitrification resistance and melting resistance of the glass are lowered, so that the content is 8% or less, preferably 5% or less, and more preferably 3% or less.

WO₃Is an optional component which can adjust the optical constants and devitrification resistance of the glass, but when the content exceeds 8%, the transmittance and devitrification resistance of the glass are lowered, and therefore, WO₃The upper limit of the content of (b) is 8%, preferably 5%, more preferably 3%, and further preferably not contained.

Ln₂O₃Is a component for increasing the refractive index of the glass and for increasing the chemical stability of the glass, is an optional component in the optical glass of the present invention, wherein Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a). By mixing Ln₂O₃The content of (2) is controlled to 10% or less, and the devitrification resistance of the glass can be improved. Thus, in the optical glass of the present invention, Ln₂O₃The upper limit of the content range is 10%, preferably 5%, more preferably 3%.

By adding 0-1% of Sb₂O₃、SnO₂SnO and CeO₂One or more components in the glass can be used as a clarifying agent to improve the clarifying effect of the glass, and 0-0.5% of the clarifying agent is preferably added. But when Sb is₂O₃When the content exceeds 1%, the glass tends to have a reduced fining property and the deterioration of the forming mold is promoted by the strong oxidation thereof, so that Sb in the present invention is₂O₃The amount of (B) is 1% or less, preferably 0.5% or less. SnO₂SnO may be added as a fining agent, but when the content exceeds 1%, the glass is colored, or when the glass is heated, softened and press-molded again, Sn tends to become a starting point of nucleation and devitrification occurs, so that the SnO of the present invention₂And SnO are contained in an amount of 1% or less, preferably 0.5% or less, and more preferably not contained. CeO (CeO)₂Action and addition amount ratio of (B) and SnO₂The content is 1% or less, preferably 0.5% or less, and more preferably not contained.

Other components not mentioned above, such as P, can be added as necessary within the range not impairing the characteristics of the glass of the present invention₂O₅、GeO₂、TeO₂、Bi₂O₃、Ta₂O₅And Ga₂O₃Etc., but the upper limit of the content of the above components contained alone or in combination is 5%, preferably 3%, more preferably 1%.

< 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 does not contain As₂O₃And PbO. Although As₂O₃Has the effects of eliminating bubbles and better preventing the glass from coloring, but As₂O₃The addition of (b) increases the platinum attack of the glass on the furnace, particularly on the platinum furnace, resulting in more platinum ions entering the glass, which adversely affects the service life of the platinum furnace. PbO can significantly improve the high-refractivity and high-dispersion properties of the glass, but PbO and As₂O₃All cause environmental pollution.

The term "not introduced", "not containing" or "0%" as used herein means that the compound, molecule or element 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 performance of the optical glass of the present invention will be described below.

< refractive index and Abbe number >

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

The refractive index (nd) of the optical glass is 1.64-1.71, preferably 1.65-1.70, more preferably 1.66-1.69; abbe number (v)_d) 35 to 40, preferably 36 to 40, and more preferably 36 to 39.

< stability against acid Effect >

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

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

< stability against Water action >

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

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

< degree of bubbling >

The bubble degree of the optical glass is tested according to the method specified in GB/T7962.8-2010.

The optical glass of the present invention has a bubble degree of B class or more, preferably A class or more, more preferably A class₀More than grade.

< degree of striae >

The degree of striae of the optical glass was measured in accordance with the method specified in MLL-G-174B. The method is that a fringe instrument composed of a point light source and a lens is used for comparing and checking with a standard sample from the direction of most easily seeing the fringes, the 4 grades are respectively A, B, C, D grades, A grade is the fringe without being seen by naked eyes under the specified detection condition, B grade is the fringe with fineness and dispersion under the specified detection condition, C grade is the slight parallel fringe under the specified detection condition, and D grade is the rough fringe under the specified detection condition.

The optical glass of the present invention has a striae of class C or more, preferably class B or more.

< upper limit temperature of crystallization >

Measuring the crystallization performance of the glass by adopting a gradient temperature furnace method, manufacturing the glass into a sample of 180 x 10mm, polishing the side surface, putting the sample into a furnace with a temperature gradient (5 ℃/cm), heating to 1400 ℃, keeping the temperature for 4 hours, taking out the sample, naturally cooling to room temperature, observing the crystallization condition of the glass under a microscope, wherein the highest temperature corresponding to the occurrence of crystals of the glass is the crystallization upper limit temperature of the glass.

The upper limit temperature of crystallization of the optical glass of the present invention is 1150 ℃ or lower, preferably 1100 ℃ or lower, and more preferably 1050 ℃ or lower.

< coefficient of thermal expansion >

Coefficient of thermal expansion (alpha)_20～120C.) according to the method specified in GB/T7962.16-2010.

The coefficient of thermal expansion (. alpha.) of the optical glass of the present invention_20～120℃) Is 85X 10^-7Preferably 80X 10 or less,/K^-7A value of 78X 10 or less, more preferably^-7and/K is less than or equal to.

< transition temperature >

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

Transition temperature (T) of the optical glass of the present invention_g) Is 600 ℃ or lower, preferably 590 ℃ or lower, more preferably 585 ℃.

< Density >

The density (. rho.) was tested according to the method specified in GB/T7962.20-2010.

The optical glass of the present invention has a density (. rho.) of 3.8g/cm³Hereinafter, it is preferably 3.7g/cm³Hereinafter, more preferably 3.6g/cm³Hereinafter, more preferably 3.5g/cm³The following.

[ production method ]

The method for manufacturing the optical glass comprises the following steps: the glass is produced by adopting conventional raw materials and conventional processes, carbonate, nitrate, sulfate, oxide and the like are used as raw materials, the materials are mixed according to a conventional method, the mixed furnace burden is put into a smelting furnace at 1350-1400 ℃ for smelting, and after clarification and full homogenization, the optical glass is cast or formed by leaking injection at 1150-1200 ℃ to obtain the optical glass. Those skilled in the art can appropriately select the raw materials, the process method and the process parameters according to the actual needs.

[ optical preform and optical element ]

The optical preform can be produced from the optical glass produced by, for example, grinding or press molding such as reheat press molding or precision press molding. That is, the optical preform may be produced by machining the optical glass by grinding, polishing, or the like, or by producing a preform for press molding from the optical glass, subjecting the preform to reheat press molding, and then polishing, or by precision press molding the preform obtained by polishing.

It should be noted that the means for producing the optical 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 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 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, display 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 2 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 2.

TABLE 1

TABLE 2

< optical 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 from the glasses obtained in examples 1 to 20 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 optical preform examples were annealed to reduce the deformation in the glass and to fine-tune the optical properties such as refractive index to 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 obtained by the above-described optical element embodiment is used for, for example, imaging devices, sensors, microscopes, medical technologies, digital projection, communications, optical communication technologies/information transmission, optics/lighting in the automobile field, photolithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, or for image pickup devices and apparatuses in the vehicle-mounted field, by forming an optical component or an optical assembly by using one or more optical elements through optical design.

Claims

1. The environment-friendly optical glass is characterized by comprising the following components in percentage by weight: SiO 2₂：30～50％、TiO₂：2～20％、ZnO：15～35％、ZrO₂：0～10％、BaO：5～24％、Na₂O：0～15％、K₂O：0～10％、Ln₂O₃: 0 to 10%, wherein ZnO/BaO is 1.2 to 5.0, and Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃One or more of (a).

2. The environmentally friendly optical glass of claim 1, further comprising, in weight percent: li₂O：0～10％、Nb₂O₅：0～8％、B₂O₃：0～10％、CaO：0～8％、SrO：0～8％、MgO：0～8％、Al₂O₃：0～8％、WO₃: 0-8% of a clarifying agent: 0-1% of a clarifying agent Sb₂O₃、SnO₂SnO and CeO₂One or more of (a).

3. The environment-friendly optical glass is characterized in that the components of the environment-friendly optical glass are expressed by weight percentage and are SiO₂：30～50％、TiO₂：2～20％、ZnO：15～35％、ZrO₂：0～10％、BaO：5～24％、Na₂O：0～15％、K₂O：0～10％、Li₂O：0～10％、Nb₂O₅：0～8％、Ln₂O₃：0～10％、B₂O₃：0～10％、CaO：0～8％、SrO：0～8％、MgO：0～8％、Al₂O₃：0～8％、WO₃: 0-8% of a clarifying agent: 0 to 1%, wherein ZnO/BaO is 1.2 to 5.0, Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂SnO and CeO₂One or more of (a).

4. According to any one of claims 1 to 3The environment-friendly optical glass is characterized in that: SiO 2₂: 35 to 50%, and/or TiO₂: 5-15%, and/or ZnO: 18 to 30%, and/or ZrO₂: 0.5-8%, and/or BaO: 8 to 22%, and/or Na₂O: 3 to 12%, and/or K₂O: 0.5 to 8%, and/or Li₂O: 0 to 5%, and/or Nb₂O₅: 0 to 5%, and/or Ln₂O₃: 0 to 5%, and/or B₂O₃: 0-5%, and/or CaO: 0-5%, and/or SrO: 0-5%, and/or MgO: 0 to 5%, and/or Al₂O₃: 0 to 5%, and/or WO₃: 0-5%, and/or a clarifying agent: 0 to 0.5%, wherein Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂SnO and CeO₂One or more of (a).

5. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: SiO 2₂: 35 to 45%, and/or TiO₂: 7-13%, and/or ZnO: 20 to 28%, and/or ZrO₂: 1-5%, and/or BaO: 10 to 18%, and/or Na₂O: 5 to 10%, and/or K₂O: 1 to 5%, and/or Li₂O: 0 to 2%, and/or Nb₂O₅: 0 to 2%, and/or Ln₂O₃: 0 to 3%, and/or B₂O₃: 0-2%, and/or CaO: 0-2%, and/or SrO: 0-2%, and/or MgO: 0 to 2%, and/or Al₂O₃: 0 to 2%, and/or WO₃: 0 to 3%, and/or Sb₂O₃: 0 to 0.5%, wherein Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃One or more of (a).

6. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: the ZnO/BaO ratio is 1.2 to 3.0.

7. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: the ZnO/BaO ratio is 1.2 to 2.5.

8. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: TiO 2₂/SiO₂0.15 to 0.5.

9. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: TiO 2₂/SiO₂0.15 to 0.4.

10. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: TiO 2₂/SiO₂0.2 to 0.35.

11. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: nb₂O₅The value of/ZnO is 0.4 or less.

12. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: nb₂O₅The value of/ZnO is 0.2 or less.

13. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: nb₂O₅The value of/ZnO is 0.1 or less.

14. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: k₂O/(Li₂O+Na₂O+K₂O) is 0.1 to 0.45.

15. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: k₂O/(Li₂O+Na₂O+K₂O) is 0.12 to 0.4.

16. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: k₂O/(Li₂O+Na₂O+K₂O) is 0.15 to 0.35.

17. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: (Na)₂O+K₂O)/BaO is 0.2 to 2.0.

18. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: (Na)₂O+K₂O)/BaO is 0.3 to 1.5.

19. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: (Na)₂O+K₂O)/BaO is 0.4 to 1.0.

20. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: (SiO)₂+ZrO₂)/(ZnO+TiO₂) 0.55 to 3.0.

21. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: (SiO)₂+ZrO₂)/(ZnO+TiO₂) 0.7 to 2.5.

22. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: (SiO)₂+ZrO₂)/(ZnO+TiO₂) 0.8 to 1.8.

23. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: BaO/(MgO + CaO + SrO + BaO) is 0.7-1.0.

24. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: BaO/(MgO + CaO + SrO + BaO) is 0.8-1.0.

25. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: BaO/(MgO + CaO + SrO + BaO) is 0.9-1.0.

26. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: (Li)₂O+ZnO)/SiO₂0.35 to 1.2.

27. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: (Li)₂O+ZnO)/SiO₂0.4 to 1.0.

28. The eco-friendly optical glass according to any one of claims 1 to 3, wherein: (Li)₂O+ZnO)/SiO₂0.45 to 0.85.

29. The eco-friendly optical glass according to any one of claims 1 to 3, wherein the eco-friendly optical glass has a refractive index nd of 1.64 to 1.71; abbe number v_dIs 35 to 40.

30. The eco-friendly optical glass according to any one of claims 1 to 3, wherein the eco-friendly optical glass has a refractive index nd of 1.65 to 1.70; abbe number v_dIs 36 to 40.

31. The eco-friendly optical glass according to any one of claims 1 to 3, wherein the refractive index of the eco-friendly optical glass isnd is 1.66-1.69; abbe number v_d36 to 39.

32. The eco-friendly optical glass according to any one of claims 1 to 3, wherein the eco-friendly optical glass has a water-resistant stability D_WIs more than 2 types; and/or stability against acid action D_AIs more than 2 types.

33. The eco-friendly optical glass according to any one of claims 1 to 3, wherein the eco-friendly optical glass has a water-resistant stability D_WIs of type 1; and/or stability against acid action D_AIs type 1.

34. The eco-friendly optical glass according to any one of claims 1 to 3, wherein the eco-friendly optical glass has a bubble degree of class B or higher; and/or the degree of streaking is at least level C.

35. The eco-friendly optical glass according to any one of claims 1 to 3, wherein the eco-friendly optical glass has a bubble degree of class A or higher; and/or the degree of streaking is above class B.

36. The eco-friendly optical glass according to any one of claims 1 to 3, wherein the eco-friendly optical glass has a bubble degree A₀More than grade.

37. The eco-friendly optical glass according to any one of claims 1 to 3, wherein the eco-friendly optical glass has a thermal expansion coefficient α_20～120℃Is 85X 10^-7below/K; and/or the upper limit temperature of crystallization is below 1150 ℃; and/or transition temperature T_gIs below 600 ℃.

38. The eco-friendly optical glass according to any one of claims 1 to 3, wherein the eco-friendly optical glass has a thermal expansion coefficient α_20～120℃Is 80X 10^-7below/K; and/or the upper limit temperature of crystallization is below 1100 ℃; and/or transition temperature T_gIs below 590 ℃.

39. The eco-friendly optical glass according to any one of claims 1 to 3, wherein the eco-friendly optical glass has a thermal expansion coefficient α_20～120℃Is 78X 10^-7below/K; and/or the upper limit temperature of crystallization is 1050 ℃ or lower; and/or transition temperature T_gIt is 585 deg.C or lower.

40. An optical preform made of the environmentally friendly optical glass as claimed in any one of claims 1 to 39.

41. An optical element made of the environmentally friendly optical glass as claimed in any one of claims 1 to 39, or an optical preform as claimed in claim 40.

42. An optical device comprising the eco-friendly optical glass according to any one of claims 1 to 39, or comprising the optical element according to claim 41.