CN109721241B

CN109721241B - Optical glass, glass preform, optical element and optical instrument

Info

Publication number: CN109721241B
Application number: CN201910204139.0A
Authority: CN
Inventors: 袁伟; 何波
Original assignee: CDGM Glass Co Ltd
Current assignee: CDGM Glass Co Ltd
Priority date: 2019-03-18
Filing date: 2019-03-18
Publication date: 2022-01-25
Anticipated expiration: 2039-03-18
Also published as: CN109721241A

Abstract

The invention provides an optical glass, which comprises the components by weight percentage：SiO₂：0～20％、B₂O₃：10～30％、La₂O₃：20～50％、Gd₂O₃：0～15％、Y₂O₃：0～15％、ZnO：12～30％、WO₃：4～20％、Nb₂O₅：0～15％、ZrO₂: 0 to 10% of WO₃the/ZnO is 0.15 to 1.5. The invention ensures that the obtained optical glass has larger positive refractive index temperature coefficient and excellent anti-crystallization performance under the condition of obtaining optical performances such as expected refractive index, Abbe number and the like through reasonable component design.

Description

Optical glass, glass preform, optical element and optical instrument

Technical Field

The invention relates to optical glass, in particular to optical glass with a refractive index of 1.75-1.85 and an Abbe number of 37-47, and a glass prefabricated member, an optical element and an optical instrument which are made of the optical glass.

Background

In the prior art, glass with a refractive index of 1.75-1.85 and an Abbe number of 37-47 belongs to high-refractive-index glass and is widely applied to various lenses. In recent years, vehicle-mounted lens devices have been developed vigorously, and compared with general photography and other applications, the quality of the vehicle-mounted lens is related to safety, so that the vehicle-mounted lens emphasizes the reliability of the device, and particularly, the vehicle-mounted lens is exposed outside a vehicle body and needs to bear severe working environments, such as a reversing camera, a front-view camera, a rearview mirror auxiliary camera and the like.

The principle of designing a vehicle-mounted lens meeting the severe working environment is that the structure is as simple as possible, and the more complex the structure is, the worse the reliability is. Therefore, in order to meet the design requirement of long service life (more than ten years) of the vehicle-mounted lens suitable for severe working environment, the optical design generally adopts the design of a fixed-focus lens, the number of lenses of the fixed-focus lens is less than that of the zoom lens, and meanwhile, a zooming driving structure is not arranged, so that the reliability is greatly improved compared with that of the zoom lens. However, although the prime lens has excellent reliability, it is applied to a vehicle, and it is very difficult to correct the temperature drift of the lens. The temperature drift of the lens means that when the temperature changes dramatically, for example, day and night temperature difference in desert area reaches 60 ℃, under the scene of very large temperature difference such as automobile driving from tropical zone to cold zone, the focal length of the lens changes, thereby causing imaging blur. For automobiles, safety is the first place, and therefore, a vehicle-mounted camera needs to keep clear imaging under the condition of rapid temperature change.

For optical designs, more different types of lens combinations and zoom systems can be used to address the temperature drift problem. However, due to the reliability requirements of the on-board system, the temperature drift problem needs to be solved on the fixed-focus imaging system with a small number of lenses (even 3 pieces), and the development of optical glass with a specific temperature refractive index is required. In the field of vehicle-mounted applications, it is currently common practice to use optical glasses with large positive and negative temperature coefficients to effectively correct temperature drift and fix focus, so that development of optical glasses with large positive temperature coefficients is required, which is a new subject for optical design and optical material research.

The requirement on the anti-crystallization performance of the optical glass is high in the production or secondary compression process of the optical glass. If the crystallization resistance of the optical glass is poor, crystals are easy to precipitate in the production process, so that the glass is discarded, and particularly, the crystallization in the secondary pressing process can cause that an optical element formed by pressing cannot be used, so that the waste of cost and energy is caused.

Disclosure of Invention

Based on the reasons, the technical problem to be solved by the invention is to provide a high-refractive-index glass with the refractive index (nd) of 1.75-1.85 and the Abbe number (v)_d) The glass is 37-47, and has a large positive refractive index temperature coefficient and excellent anti-crystallization performance.

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

(1) the optical glass comprises the following components in percentage by weight: SiO 2₂：0～20％、B₂O₃：10～30％、La₂O₃：20～50％、Gd₂O₃：0～15％、Y₂O₃：0～15％、ZnO：12～30％、WO₃：4～20％、Nb₂O₅：0～15％、ZrO₂: 0 to 10% of WO₃the/ZnO is 0.15 to 1.5.

(2) The optical glass according to (1), which comprises the following components in percentage by weight: TiO 2₂: 0 to 10%, and/or Al₂O₃: 0 to 8%, and/or Ta₂O₅: 0 to 10%, and/or P₂O₅：0～10％、And/or Yb₂O₃: 0-10%, and/or RO: 0 to 20%, and/or Rn₂O: 0-10%, and/or a clarifying agent: 0-1%, wherein RO is one or more of MgO, CaO, SrO and BaO, and Rn₂O is Li₂O、Na₂O and K₂One or more of O and Sb as clarifier₂O₃、SnO₂SnO and CeO₂One or more of (a).

(3) Optical glass, the composition of which is expressed in weight percent and is made of SiO₂：0～20％、B₂O₃：10～30％、La₂O₃：20～50％、Gd₂O₃：0～15％、Y₂O₃：0～15％、ZnO：12～30％、WO₃：4～20％、Nb₂O₅：0～15％、ZrO₂：0～10％、TiO₂：0～10％、Al₂O₃：0～8％、Ta₂O₅：0～10％、P₂O₅：0～10％、Yb₂O₃：0～10％、RO：0～20％、Rn₂O: 0-10% of a clarifying agent: 0 to 1% of a composition, wherein WO₃0.15-1.5 of/ZnO, one or more of MgO, CaO, SrO and BaO of RO, and Rn₂O is Li₂O、Na₂O and K₂One or more of O and Sb as clarifier₂O₃、SnO₂SnO and CeO₂One or more of (a).

(4) Optical glass, the composition of which is expressed in weight percentage and contains SiO₂And B₂O₃And B is₂O₃The content is more than SiO₂Content (c); containing WO₃、Nb₂O₅And ZnO, wherein, WO₃0.15 to 1.5 of/ZnO, and WO₃/Nb₂O₅Is more than 0.5; the refractive index nd of the optical glass is 1.75-1.85, and the Abbe number vd is 37-47.

(5) The optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: SiO 2₂: 3 to 15%, and/or B₂O₃: 12 to 25%, and/or La₂O₃: 25 to 45%, and/or Gd₂O₃: 0 to 10%, and/or Y₂O₃: 0.5-10%, and/or ZnO: 15 to 25%, and/or WO₃: 5 to 15%, and/or Nb₂O₅: 1 to 10%, and/or ZrO₂: 1 to 8%, and/or TiO₂: 0 to 8%, and/or Al₂O₃: 0 to 5%, and/or Ta₂O₅: 0 to 5%, and/or P₂O₅: 0 to 5% and/or Yb₂O₃: 0-5%, and/or RO: 0 to 10%, and/or Rn₂O: 0-5%, and/or a clarifying agent: 0-0.5%, wherein RO is one or more of MgO, CaO, SrO and BaO, and Rn₂O is Li₂O、Na₂O and K₂One or more of O and Sb as clarifier₂O₃、SnO₂SnO and CeO₂One or more of (a).

(6) The optical glass according to any one of (1) to (3), which comprises the following components in percentage by weight: b is₂O₃The content is more than SiO₂Content (c); and/or WO₃/Nb₂O₅Is 0.5 or more.

(7) The optical glass according to any one of (1) to (4), which has a composition satisfying, as a percentage by weight, one or more of the following 5 conditions:

1)ZnO/La₂O₃0.25 to 1.3;

2)ZnO/B₂O₃0.45 to 2.75;

3)WO₃/(SiO₂+B₂O₃) 0.1 to 1.0;

4)Nb₂O₅+TiO₂+WO₃：5～40％；

5)La₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) 0.5 to 1.0.

(8) The optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: SiO 2₂: 5 to 12%, and/or B₂O₃: 15-21% and/or La₂O₃: 30 to 42%, and/or Gd₂O₃: 0 to 5%, and/or Y₂O₃: 1-6%, and/or ZnO: 16-23%, and/or WO₃: 5 to 12%, and/or Nb₂O₅: 2.5 to 8%, and/or ZrO₂: 1.5 to 5%, and/or TiO₂: 0 to 3%, and/or Al₂O₃: 0 to 3%, and/or Ta₂O₅: 0 to 3%, and/or P₂O₅: 0 to 3% and/or Yb₂O₃: 0-2%, and/or RO: 0 to 5%, and/or Rn₂O: 0-3%, and/or a clarifying agent: 0-0.1%, wherein RO is one or more of MgO, CaO, SrO and BaO, and Rn₂O is Li₂O、Na₂O and K₂One or more of O and Sb as clarifier₂O₃、SnO₂SnO and CeO₂One or more of (a).

(9) The optical glass according to any one of (1) to (4), which has a composition satisfying, as a percentage by weight, one or more of the following 7 conditions:

1)WO₃the/ZnO is 0.2-1.0;

2)WO₃/Nb₂O₅0.8 to 10;

3)ZnO/La₂O₃0.3 to 1.0;

4)ZnO/B₂O₃0.6 to 2.0;

5)WO₃/(SiO₂+B₂O₃) 0.13 to 0.8;

6)Nb₂O₅+TiO₂+WO₃：7～30％；

7)La₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) 0.6 to 1.0.

(10) The optical glass according to any one of (1) to (4), which has a composition satisfying, as a percentage by weight, one or more of the following 7 conditions:

1)WO₃the/ZnO is 0.25-0.75;

2)WO₃/Nb₂O₅1.0 to 6.0;

3)ZnO/La₂O₃0.4 to 0.8;

4)ZnO/B₂O₃0.75 to 1.5;

5)WO₃/(SiO₂+B₂O₃) 0.15 to 0.5;

6)Nb₂O₅+TiO₂+WO₃：8～20％；

7)La₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) 0.75 to 1.0.

(11) The optical glass according to any one of (1) to (4), wherein the refractive index (nd) of the optical glass is 1.75 to 1.85, preferably 1.77 to 1.83, and more preferably 1.78 to 1.82; abbe number (v)_d) Is 37 to 47, preferably 38 to 45, and more preferably 39 to 44.

(12) The optical glass according to any one of (1) to (4), wherein the temperature coefficient of refractive index (dn/dt) of the optical glass at 40 to 60 ℃ is 7.0X 10^-6/. degree.C or higher, preferably 8.0X 10^-6/. degree.C.or higher, more preferably 9.0X 10^-6Preferably 9.5X 10 ℃ or higher^-6Above/° c.

(13) The optical glass according to any one of (1) to (4), which has stability against water action (D)_W) Is 2 or more, preferably 1; and/or a degree of bubbling of B class or more, preferably A class or more, more preferably A₀More preferably A or more₀₀A stage; and/or the upper crystallization temperature is 1150 ℃ or lower, preferably 1100 ℃ or lower, and more preferably 1050 ℃ or lower; and/or transition temperature (T)_g) Is 620 ℃ or lower, preferably 615 ℃ or lower, more preferably 610 ℃ or lower; and/or lambda₈₀Less than or equal to 410nm, preferably lambda₈₀Less than or equal to 405nm, more preferably lambda₈₀Less than or equal to 400 nm; and/or lambda₅Less than or equal to 350nm, preferably lambda₅Less than or equal to 345nm, more preferably lambda₅Less than or equal to 342 nm.

The present invention also provides a glass preform comprising:

(14) a glass preform made of the optical glass according to any one of (1) to (13).

The present invention also provides an optical element:

(15) an optical element produced from the optical glass according to any one of (1) to (13), or the glass preform according to (14).

The present invention also provides an optical instrument:

(16) an optical device comprising the optical glass according to any one of (1) to (13) or the optical element according to (15).

The invention has the beneficial effects that: the invention ensures that the obtained optical glass has larger positive refractive index temperature coefficient and excellent anti-crystallization performance under the condition of obtaining optical performances such as expected refractive index, Abbe number and the like through reasonable component design.

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. Note that, although the description of the duplicate description may be appropriately omitted, the gist of the invention is not limited to this. The optical glass of the present invention may be simply referred to as glass in the following.

[ 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 >

B₂O₃Is an indispensable component for forming the glass of the present invention, by containing 10% or more of B₂O₃The devitrification resistance of the glass can be improved, and the formation of stable glass is promoted; but when B is₂O₃The content exceeding 30% lowers the refractive index of the glass and lowers the chemical stability of the glass, so that B in the present invention₂O₃The content is 10 to 30%, preferably 12 to 25%, more preferably 15 to 21%.

SiO₂Has the effect of improving the thermal stability of the glass, is effective in obtaining a viscosity suitable for forming when forming a glass solution, and when the content exceeds 20%, the melting property of the glass is deteriorated and the transition temperature is increased, so that 0 to 20% of SiO is introduced in the present invention₂In some embodiments, by introducing 3% or more of SiO₂Since the devitrification resistance and chemical durability of the glass can be improved, it is preferable to introduce 3 to 15% of SiO into the glass₂Further preferably, 5-12% of SiO is introduced₂。

The inventors have found through a large number of experimental studies that, in the optical glass of the present invention, B₂O₃The content is more than SiO₂At levels that increase the chemical stability and devitrification resistance of the glass, therefore in some embodiments, B is preferred₂O₃The content is more than SiO₂And (4) content.

La₂O₃Has the effect of increasing the refractive index and maintaining low dispersion, and if the content thereof is less than 20%, it is difficult to achieve the above effect; when the content exceeds 50%, the thermal stability of the glass is lowered and the glass transition temperature tends to be increased. In the present invention, La₂O₃The content of (b) is controlled within a range of 20 to 50%, preferably 25 to 45%, and more preferably 30 to 42%.

Gd₂O₃Having an increased refractive indexWhen the content exceeds 15%, devitrification resistance of the glass tends to be lowered and the transition temperature tends to be increased, so that Gd in the present invention₂O₃The content of (b) is 15% or less, preferably 0 to 10%, more preferably 0 to 5%.

Y₂O₃Since the refractive index of the glass is increased while maintaining low dispersion, and when the content exceeds 15%, the thermal stability and chemical stability of the glass are lowered, Y in the present invention₂O₃The content of (B) is 15% or less. In some embodiments, by introducing 0.5% or more Y₂O₃Since the degree of striae of the glass can be optimized while maintaining the refractive index of the glass, Y is preferable in the present invention₂O₃The content of (B) is 0.5 to 10%, more preferably 1 to 6%.

In the invention, less than 10% of Yb is introduced₂O₃It is preferable that Yb is a glass having a desired optical constant and maintaining the devitrification resistance of the glass₂O₃The content of (b) is 0 to 5%, more preferably 0 to 2%, and further preferably no incorporation.

The inventor has found that in the lanthanide optical glass, La₂O₃、Gd₂O₃、Y₂O₃The ratio of (A) to (B) may affect the devitrification resistance and the coloring degree of the glass, and further, when La is used₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) When the value of (A) is in the range of 0.5 to 1.0, the glass can have a desired refractive index and Abbe number and can have improved devitrification resistance and coloring degree, and preferably La₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) The value of (A) is 0.6 to 1.0, more preferably La₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) The value of (A) is 0.75 to 1.0, and La is more preferable₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) The value of (b) is 0.8 to 1.0.

ZnO has the effects of reducing the glass transition temperature and improving the chemical stability, and by introducing more than 12 percent of ZnO, the invention can fully obtain the above effects and simultaneously improve the temperature coefficient of the refractive index of the glass; however, when the content of ZnO exceeds 30%, the devitrification resistance of the glass is lowered. Therefore, the content of ZnO in the invention is 12 to 30%, preferably 15 to 25%, and more preferably 16 to 23%.

In some embodiments, ZnO and La₂O₃The introduction ratio of (A) affects the glass transition temperature and the bubble degree, and further, when ZnO/La is used₂O₃At 0.25 or less, the glass transition temperature increases and the bubble degree decreases; when ZnO/La₂O₃When the ratio is 1.3 or more, it is difficult to control the optical constants of the glass to the desired range, so that ZnO/La is used in the present invention₂O₃The range is 0.25 to 1.3, and ZnO/La is preferred₂O₃When the range is 0.3-1.0, the bubble degree of the glass can easily reach A₀Higher order, more preferably ZnO/La₂O₃The range is 0.4 to 0.8.

In some embodiments, when ZnO and B are used₂O₃Content ratio of ZnO/B₂O₃When the ratio is 0.45 or less, the chemical stability of the glass is lowered, and when the ratio is ZnO/B₂O₃When the glass content is 2.75 or more, the glass forming stability is deteriorated, the meltability is deteriorated, and the striae are reduced. Thus, ZnO/B₂O₃The range of (A) is 0.45 to 2.75, preferably 0.6 to 2.0, and more preferably 0.75 to 1.5.

WO₃It is effective for adjusting optical constants and improving resistance to devitrification, and the temperature coefficient of refractive index of the glass can be increased, and if the content thereof is less than 4%, the above-mentioned effects cannot be sufficiently obtained. In some embodiments, WO₃When the content is 5% or more, the thermal expansion coefficient can be reduced, and the glass can be prevented from being broken in a processing step accompanied by a temperature change such as precision pressing. When WO is₃When the content exceeds 20%, the light transmittance of the glass in a short wavelength region of a visible light region is deteriorated, and the tendency of coloring of the glass is increased. Thus, WO in the present invention₃The content of (b) is 4 to 20%, preferably 5 to 15%, more preferably 5 to 12%.

In bookIn the invention, when WO is used₃Incorporation ratio to ZnO content WO₃When the/ZnO content is more than 1.5, the glass tends to be deteriorated in the coloring degree; when WO is₃When the content of ZnO is less than 0.15, the bubble content of the glass decreases, and further, when WO is added₃When the/ZnO is within the range of 0.15-1.5, the expected temperature coefficient of the refractive index can be easily obtained. Thus WO in the present invention₃The amount of/ZnO is 0.15 to 1.5, preferably 0.2 to 1.0, and more preferably 0.25 to 0.75.

WO₃Introduction amount of (2) and skeleton component SiO₂And B₂O₃The amount of the glass has an influence on the temperature coefficient of refractive index, chemical stability and devitrification resistance of the glass, and further, when WO is applied₃/(SiO₂+B₂O₃) When the refractive index is less than 0.1, the temperature coefficient of the refractive index of the glass is lowered; when WO is₃/(SiO₂+B₂O₃) Above 1.0, the chemical stability and devitrification resistance of the glass are deteriorated, so that WO in the present invention₃/(SiO₂+B₂O₃) The range of (A) is 0.1 to 1.0, preferably 0.13 to 0.8, and more preferably 0.15 to 0.5.

Nb₂O₅Is a component for improving the devitrification resistance, chemical durability, refractive index and lowering the Abbe number of the glass. When the content exceeds 15%, the thermal stability of the glass is lowered and the liquidus temperature tends to rise, so that Nb in the present invention₂O₅The content of (B) is 15% or less. In some embodiments, by containing more than 1% Nb₂O₅It is possible to easily obtain a high temperature coefficient of refractive index and a lower thermal expansion coefficient, and it has an effect of preventing glass breakage in a processing step accompanied by temperature change such as precision pressing, and Nb is preferable₂O₅The content is 1 to 10%, more preferably 2.5 to 8%.

In the present invention, WO is preferred₃/Nb₂O₅When the amount is 0.5 or more, the glass can easily obtain a desired high temperature coefficient of refractive index, and the glass is excellent in the degree of coloration and the devitrification resistance, and WO is more preferable₃/Nb₂O₅Is 0.8 to 10, and more preferably 1.0 to 6.0.

Small amount ofZrO₂The addition of the ZrO in the glass can improve the devitrification resistance and the chemical stability of the glass, and simultaneously, the proper amount of ZrO is added₂Can obviously reduce the erosion of the glass liquid to the refractory material in the production process and improve the temperature coefficient of the refractive index of the glass. However, if ZrO₂At a content exceeding 10%, the glass becomes difficult to melt and the devitrification resistance is rapidly lowered, so that ZrO in the present invention₂The content is limited to 10% or less, preferably 1 to 8%, more preferably 1.5 to 5%.

TiO₂The glass has the effect of improving the refractive index of the glass, can participate in the formation of a glass network, and is more stable when being introduced in a proper amount, but the glass dispersion is remarkably increased after the introduction, the transmittance of a short wave part in a visible light region of the glass is reduced, and the coloring tendency of the glass is increased. Thus, the TiO of the present invention₂The content of (B) is 0 to 10%, preferably 0 to 8%, more preferably 0 to 3%.

Nb₂O₅、TiO₂And WO₃Is effective for improving the refractive index and dispersion of the optical glass when the total content of Nb₂O₅+TiO₂+WO₃Below 5%, it is difficult for the glass to obtain the desired refractive index and high temperature coefficient of refractive index, and when Nb is used₂O₅+TiO₂+WO₃Above 40%, the refractive index of the glass exceeds the design requirement, and the degree of coloration and devitrification resistance deteriorate. Therefore, Nb in the present invention₂O₅+TiO₂+WO₃The content is limited to 5 to 40%, preferably 7 to 30%, more preferably 8 to 20%

Rn₂O(Rn₂O is Li₂O、Na₂O or K₂One or more of O) can improve the meltability of the glass and lower the glass transition temperature, and when the content of O exceeds 10%, the stability of the glass is deteriorated and the refractive index and the temperature coefficient of the refractive index are greatly lowered, so that Rn of the invention₂The O content is 0 to 10%, preferably 0 to 5%, more preferably 0 to 3%, and further preferably no introduction.

RO (RO is one or more of BaO, SrO, CaO, or MgO) improves the meltability of the glass and lowers the glass transition temperature, but when the content thereof exceeds 20%, the devitrification resistance of the glass is lowered and the temperature coefficient of refractive index is lowered. Therefore, the RO content of the present invention is 0 to 20%, preferably 0 to 10%, and more preferably 0 to 5%.

Ta₂O₅Has the functions of improving the refractive index and improving the devitrification resistance of the glass, but compared with other components, Ta₂O₅The price of (2) is very expensive, and the amount of use should be minimized from the practical and cost viewpoints. Thus, Ta of the present invention₂O₅The content is limited to 0 to 10%, preferably 0 to 5%, and more preferably 0 to 3%.

Introducing small amount of Al₂O₃The Al of the present invention can improve the stability and chemical stability of the formed glass, but when the content exceeds 8%, the glass tends to be deteriorated in meltability and to be lowered in devitrification resistance, so that the Al of the present invention₂O₃The content of (b) is 0 to 8%, preferably 0 to 5%, more preferably 0 to 3%.

P₂O₅Is an optional component which can improve the devitrification resistance of the glass, particularly by reacting P₂O₅The content of (A) is 10% or less, and the reduction of the chemical durability, particularly the water resistance, of the glass can be suppressed. Thus, P₂O₅The content is limited to 10% or less, preferably 5% or less, more preferably 3% or less, and further preferably not incorporated.

By adding 0-1% of Sb₂O₃、SnO₂SnO and CeO₂One or more components of the glass can be used as a clarifying agent to improve the clarifying effect of the glass. However, the invention has reasonable formula design, good clarification effect and excellent bubble degree, so that 0-0.5% of clarifier is preferably added, 0-0.1% of clarifier is more preferably added, and no clarifier is further preferably introduced.

F can reduce glass dispersion, promote glass transmissivity, improve glass anti devitrification performance, but its volatilization in smelting and forming process can make the data fluctuation of glass grow, and F's volatilization can lead to the production of stripe in forming process simultaneously. In addition, volatilization of F can pose a potential safety threat to humans and the environment. In the present invention, the content of F is limited to 5% or less, and preferably is not incorporated.

< 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 1.75-1.85, preferably 1.77-1.83, and more preferably 1.78-1.82; abbe number (v)_d) Is 37 to 47, preferably 38 to 45, and more preferably 39 to 44.

< 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 preferably A or more₀₀And (4) stages.

< 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.

< temperature coefficient of refractive index >

The temperature coefficient of refractive index (d-line dn/dt relative) (10) of optical glass in the range of 40 to 60 ℃ was measured according to the method prescribed in GB/T7962.4-2010^-6/℃))

The temperature coefficient of refractive index (dn/dt) of the optical glass is 7.0 multiplied by 10^-6/. degree.C or higher, preferably 8.0X 10^-6/. degree.C.or higher, more preferably 9.0X 10^-6Preferably 9.5X 10 ℃ or higher^-6Above/° c.

< 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 620 ℃ or lower, preferably 615 ℃ or lower, and more preferably 610 ℃ or lower.

< degree of coloration >

Coloring degree (. lamda.) for short-wave transmission spectral characteristics of the glass of the present invention₈₀/λ₅) And (4) showing. Lambda [ alpha ]₈₀Refers to the wavelength, lambda, corresponding to a glass having a transmittance of 80%₅The wavelength corresponding to the glass transmittance of 5% is referred to. Wherein λ is₈₀Was 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 colored very little.

Optical glass lambda of the present invention₈₀In the range of less than or equal to 410nm, preferably λ₈₀In the range of 405nm or less, more preferably lambda₈₀Is less than or equal to 400 nm. Lambda [ alpha ]₅In the range of less than or equal to 350nm, preferably λ₅In the range of 345nm or less, more preferably λ₅Is less than or equal to 342 nm.

[ 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, hydroxide, 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 1300-1400 ℃ for smelting, and after clarification, stirring and homogenization, homogeneous molten glass without bubbles and undissolved substances is obtained, and the molten glass is cast in a mold 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, for example, grinding or press molding such as reheat press molding or precision press molding. That is, the glass 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 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, 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

< 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 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. Optical glass, characterized in that its components, expressed in weight percent, contain: SiO 2₂：5.34～20％、B₂O₃：10～30％、La₂O₃：25～50％、Gd₂O₃：0～10％、Y₂O₃：0～15％、ZnO：12～30％、WO₃：4～20％、Nb₂O₅：0～15％、ZrO₂: 0 to 10% of WO₃0.15 to 1.5 of/ZnO, and WO₃/Nb₂O₅1.257-10.

2. The optical glass according to claim 1, wherein the composition further comprises, in weight percent: TiO 2₂: 0 to 10%, and/or Al₂O₃: 0 to 8%, and/or Ta₂O₅: 0 to 10%, and/or P₂O₅: 0 to 10% and/or Yb₂O₃: 0-10%, and/or RO: 0 to 20%, and/or Rn₂O: 0-10%, and/or a clarifying agent: 0-1%, wherein RO is one or more of MgO, CaO, SrO and BaO, and Rn₂O is Li₂O、Na₂O and K₂One or more of O and Sb as clarifier₂O₃、SnO₂SnO and CeO₂One or more of (a).

3. Optical glass, characterized in that its composition, expressed in weight percentage, is represented by SiO₂：5.34～20％、B₂O₃：10～30％、La₂O₃：25～50％、Gd₂O₃：0～10％、Y₂O₃：0～15％、ZnO：12～30％、WO₃：4～20％、Nb₂O₅：0～15％、ZrO₂：0～10％、TiO₂：0～10％、Al₂O₃：0～8％、Ta₂O₅：0～10％、P₂O₅：0～10％、Yb₂O₃：0～10％、RO：0～20％、Rn₂O: 0-10% of a clarifying agent: 0 to 1% of a composition, wherein WO₃0.15 to 1.5 of/ZnO, and WO₃/Nb₂O₅1.257-10, RO is one or more of MgO, CaO, SrO and BaO, Rn₂O is Li₂O、Na₂O and K₂One or more of O and Sb as clarifier₂O₃、SnO₂SnO and CeO₂One or more of (a).

4. Optical glass, characterized in that its composition, expressed in weight percent, contains SiO₂：5.34～20％、B₂O₃：10～30％、La₂O₃：25～50％、ZnO：12～30％、WO₃：4～20％、Gd₂O₃: 0 to 10%, and B₂O₃The content is more than SiO₂Content (c); containing Nb₂O₅Wherein, WO₃0.15 to 1.5 of/ZnO, and WO₃/Nb₂O₅1.257 to 10; the refractive index nd of the optical glass is 1.75-1.85, and the Abbe number vd is 37-47.

5. An optical glass according to any one of claims 1 to 4, characterised in that it comprises, in weight percent: SiO 2₂: 5.34-15%, and/or B₂O₃: 12 to 25%, and/or La₂O₃: 25 to 45%, and/or Y₂O₃: 0.5-10%, and/or ZnO: 15 to 25%, and/or WO₃: 5 to 15%, and/or Nb₂O₅: 1 to 10%, and/or ZrO₂: 1 to 8%, and/or TiO₂: 0 to 8%, and/or Al₂O₃: 0 to 5%, and/or Ta₂O₅: 0 to 5%, and/or P₂O₅: 0 to 5% and/or Yb₂O₃: 0-5%, and/or RO: 0 to 10%, and/or Rn₂O: 0-5%, and/or a clarifying agent: 0-0.5%, wherein RO is one or more of MgO, CaO, SrO and BaO, and Rn₂O is Li₂O、Na₂O and K₂One or more of O and Sb as clarifier₂O₃、SnO₂SnO and CeO₂One or more of (a).

6. An optical glass according to any one of claims 1 to 3, characterised in that it comprises, in percentages by weight: b is₂O₃The content is more than SiO₂And (4) content.

7. An optical glass according to any one of claims 1 to 4, wherein the composition, expressed in weight percent, satisfies one or more of the following 5 conditions:

1)ZnO/La₂O₃0.25 to 1.3;

2)ZnO/B₂O₃0.45 to 2.75;

3)WO₃/(SiO₂+B₂O₃) 0.1 to 1.0;

4)Nb₂O₅+TiO₂+WO₃：5～40％；

5)La₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) 0.5 to 1.0.

8. An optical glass according to any one of claims 1 to 4, characterised in that it comprises, in weight percent: SiO 2₂: 5.34-12%, and/or B₂O₃: 15-21% and/or La₂O₃: 30 to 42%, and/or Gd₂O₃: 0 to 5%, and/or Y₂O₃: 1-6%, and/or ZnO: 16-23%, and/or WO₃: 5 to 12%, and/or Nb₂O₅: 2.5 to 8%, and/or ZrO₂: 1.5 to 5%, and/or TiO₂: 0 to 3%, and/or Al₂O₃: 0 to 3%, and/or Ta₂O₅: 0 to 3%, and/or P₂O₅: 0 to 3% and/or Yb₂O₃: 0-2%, and/or RO: 0 to 5%, and/or Rn₂O: 0-3%, and/or a clarifying agent: 0-0.1%, wherein RO is one or more of MgO, CaO, SrO and BaO, and Rn₂O is Li₂O、Na₂O and K₂One or more of O and Sb as clarifier₂O₃、SnO₂SnO and CeO₂One or more of (a).

9. An optical glass according to any one of claims 1 to 4, wherein the composition, expressed in weight percent, satisfies one or more of the following 6 conditions:

1)WO₃the/ZnO is 0.2-1.0;

2)ZnO/La₂O₃0.3 to 1.0;

3)ZnO/B₂O₃0.6 to 2.0;

4)WO₃/(SiO₂+B₂O₃) 0.13 to 0.8;

5)Nb₂O₅+TiO₂+WO₃：7～30％；

6)La₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) 0.6 to 1.0.

10. An optical glass according to any one of claims 1 to 4, wherein the composition, expressed in weight percent, satisfies one or more of the following 7 conditions:

1)WO₃the/ZnO is 0.25-0.75;

2)WO₃/Nb₂O₅1.257 to 6.0;

3)ZnO/La₂O₃0.4 to 0.8;

4)ZnO/B₂O₃0.75 to 1.5;

5)WO₃/(SiO₂+B₂O₃) 0.15 to 0.5;

6)Nb₂O₅+TiO₂+WO₃：8～20％；

7)La₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) 0.75 to 1.0.

11. An optical glass according to any one of claims 1 to 3, wherein the optical glass has a refractive index nd of 1.75 to 1.85; the Abbe number vd is 37-47.

12. An optical glass according to any one of claims 1 to 4, wherein the optical glass has a refractive index nd of 1.77 to 1.83; the Abbe number vd is 38-45.

13. An optical glass according to any one of claims 1 to 4, wherein the optical glass has a refractive index nd of 1.78 to 1.82; the Abbe number vd is 39-44.

14. According toThe optical glass according to any one of claims 1 to 4, wherein the optical glass has a temperature coefficient of refractive index dn/dt at 40 to 60 ℃ of 7.0 x 10^-6Above/° c.

15. The optical glass according to any one of claims 1 to 4, wherein the optical glass has a temperature coefficient of refractive index dn/dt of 8.0 x 10 at 40 to 60 ℃^-6Above/° c.

16. The optical glass according to any one of claims 1 to 4, wherein the optical glass has a temperature coefficient of refractive index dn/dt at 40 to 60 ℃ of 9.0 x 10^-6Above/° c.

17. The optical glass according to any one of claims 1 to 4, wherein the optical glass has a temperature coefficient of refractive index dn/dt at 40 to 60 ℃ of 9.5 x 10^-6Above/° c.

18. The optical glass according to any one of claims 1 to 4, wherein the optical glass has a stability to water action D_WIs more than 2 types; and/or the bubble degree is more than B level; and/or the upper limit temperature of crystallization is below 1150 ℃; and/or transition temperature T_gBelow 620 ℃; and/or lambda₈₀Less than or equal to 410 nm; and/or lambda₅Less than or equal to 350 nm.

19. The optical glass according to any one of claims 1 to 4, wherein the optical glass has a stability to water action D_WIs of type 1; and/or the bubble degree is above A level; and/or the upper limit temperature of crystallization is below 1100 ℃; and/or transition temperature T_gBelow 615 ℃; and/or lambda₈₀Less than or equal to 405 nm; and/or lambda₅Less than or equal to 345 nm.

20. An optical glass according to any one of claims 1 to 4, whereinThe optical glass has a bubble degree of A₀More than grade; and/or the upper limit temperature of crystallization is 1050 ℃ or lower; and/or transition temperature T_gBelow 610 ℃; and/or lambda₈₀Less than or equal to 400 nm; and/or lambda₅Less than or equal to 342 nm.

21. The optical glass according to any one of claims 1 to 4, wherein the optical glass has a bubble degree A₀₀And (4) stages.

22. A glass preform made of the optical glass according to any one of claims 1 to 21.

23. An optical element produced from the optical glass according to any one of claims 1 to 21 or the glass preform according to claim 22.

24. An optical device comprising the optical glass according to any one of claims 1 to 21, or comprising the optical element according to claim 23.