CN109721241A - Optical glass, gas preform, optical element and optical instrument - Google Patents

Abstract

The present invention provides a kind of optical glass, and component indicates by weight percentage, contains: 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%, wherein WO₃/ ZnO is 0.15~1.5.The present invention is designed by reasonable component, in the case where obtaining the optical properties such as desired refractive index and Abbe number, the optical glass obtained is enable to have larger positive refracting power temperature coefficient and excellent devitrification resistance.

Description

Optical glass, gas preform, optical element and optical instrument

Technical field

It is 1.75~1.85 more particularly, to a kind of refractive index the present invention relates to a kind of optical glass, Abbe number is 37~ 47 optical glass, and the gas preform made of the optical glass, optical element and optical instrument.

Background technique

In the prior art, the glass that refractive index is 1.75~1.85, Abbe number is 37~47 belongs to glass of high refractive index, It widely applies in all kinds of camera lenses.In recent years, on-vehicle lens equipment has obtained vigorous growth, applies phase with generally photography etc. Than, the quality of on-vehicle lens is closely bound up with safety, therefore on-vehicle lens more emphasize the reliability of equipment, it is especially exposed Outside car body, need to bear harsh environments, such as backup camera, forward sight camera, rearview mirror second camera head.

It is that structure is simple as far as possible that design, which meets the principle of harsh environments on-vehicle lens, and structure is more complicated, reliably Property is poorer.Therefore, in order to meet the design of the on-vehicle lens long-life (up to 10 years or more) for being suitable for harsh environments It is required that generally being designed using tight shot in optical design, number of lenses is fewer than zoom lens, while not having zoom drive Structure, therefore reliability is improved significantly compared with zoom lens.But although tight shot reliability is very good, application On vehicle-mounted, fatal weakness is that it is very difficult for correcting the temperature drift of camera lens.The temperature drift of camera lens, which refers to, works as When acute variation occurs for temperature, for example the day and night temperature of desert area reaches 60 DEG C, and automobile drives to the temperature difference such as frigid zone from the torrid zone Under very big scene, the focal length of camera lens can change, so as to cause image blur.It is first safely for automobile Position, therefore, vehicle-mounted camera needs under conditions of temperature change dramatically, is able to maintain and is clearly imaged.

For optical design, it can usually be solved using more different types of lens combinations and zoom system, pancreatic system Temperature drift problems.But the requirement due to onboard system to reliability, it needs in number of lenses seldom (even 3) Temperature drift problems are solved in fixed-focus imaging system, this just needs to develop the optical glass with special temperature refraction rate coefficient. The current widespread practice of automotive field is the optics glass that will have larger positive refracting power temperature coefficient and negative index temperature coefficient Glass is applied in combination, and can effectively correct temperature drift, fixed-focus, it is therefore desirable to which developing has larger positive refracting power temperature coefficient Optical glass, this is also the new issue researching and proposing to optical design and optical material of development in epoch.

Optical glass can require height during production or secondary press, to the devitrification resistance of optical glass.Optical glass If devitrification resistance can be bad, it is easy to precipitate crystal in process of production, leads to the discarded of glass, especially in secondary press process Middle crystallization, will lead to the optical element that compacting is formed cannot use, and cause the waste of cost and the energy.

Summary of the invention

Based on the above reasons, technical problem to be solved by the invention is to provide a kind of refractive index (nd) be 1.75~ 1.85, Abbe number (ν_d) it is 37~47, and the optics glass with larger positive refracting power temperature coefficient and excellent devitrification resistance energy Glass.

The technical proposal for solving the technical problem of the invention is:

(1) optical glass, component indicate by weight percentage, contain: 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%, wherein WO₃/ ZnO is 0.15~1.5.

(2) optical glass according to (1), component indicates by weight percentage, also contains: TiO₂: 0~10%, And/or Al₂O₃: 0~8%, and/or Ta₂O₅: 0~10%, and/or P₂O₅: 0~10%, and/or Yb₂O₃: 0~10%, and/or RO:0~20%, and/or Rn₂O:0~10%, and/or clarifying agent: 0~1%, wherein RO is in MgO, CaO, SrO and BaO It is one or more, Rn₂O is Li₂O、Na₂O and K₂One of O or a variety of, clarifying agent Sb₂O₃、SnO₂, SnO and CeO₂In one Kind is a variety of.

(3) optical glass, component indicate by weight percentage, by 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%, clarifying agent: 0~1% forms, wherein WO₃/ ZnO be 0.15~1.5, RO MgO, CaO, SrO and One of BaO or a variety of, Rn₂O is Li₂O、Na₂O and K₂One of O or a variety of, clarifying agent Sb₂O₃、SnO₂, SnO and CeO₂One of or it is a variety of.

(4) optical glass, component indicate by weight percentage, contain SiO₂And B₂O₃, and B₂O₃Content is greater than SiO₂Contain Amount；Contain WO₃、Nb₂O₅And ZnO, wherein WO₃/ ZnO is 0.15~1.5, WO₃/Nb₂O₅It is 0.5 or more；The optical glass Refractive index nd is 1.75~1.85, and Abbe number vd is 37~47.

(5) according to any optical glass in (1)~(4), component indicates by weight percentage, in which: SiO₂: 3 ~15%, and/or B₂O₃: 12~25%, and/or La₂O₃: 25~45%, and/or Gd₂O₃: 0~10%, and/or Y₂O₃: 0.5~ 10%, and/or ZnO:15~25%, and/or WO₃: 5~15%, and/or Nb₂O₅: 1~10%, and/or ZrO₂: 1~8%, And/or TiO₂: 0~8%, and/or Al₂O₃: 0~5%, and/or Ta₂O₅: 0~5%, and/or P₂O₅: 0~5%, and/or Yb₂O₃: 0~5%, and/or RO:0~10%, and/or Rn₂O:0~5%, and/or clarifying agent: 0~0.5%, wherein RO be One of MgO, CaO, SrO and BaO or a variety of, Rn₂O is Li₂O、Na₂O and K₂One of O or a variety of, clarifying agent are Sb₂O₃、SnO₂, SnO and CeO₂One of or it is a variety of.

(6) according to any optical glass in (1)~(3), component indicates by weight percentage, in which: B₂O₃Content Greater than SiO₂Content；And/or WO₃/Nb₂O₅It is 0.5 or more.

(7) according to any optical glass in (1)~(4), component indicates by weight percentage, meets 5 kinds following One of situation or more than one:

1)ZnO/La₂O₃It is 0.25~1.3；

2)ZnO/B₂O₃It is 0.45~2.75；

3)WO₃/(SiO₂+B₂O₃) it is 0.1~1.0；

4)Nb₂O₅+TiO₂+WO₃: 5~40%；

5)La₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) it is 0.5~1.0.

(8) according to any optical glass in (1)~(4), component indicates by weight percentage, in which: SiO₂: 5 ~12%, and/or B₂O₃: 15~21%, and/or La₂O₃: 30~42%, and/or Gd₂O₃: 0~5%, and/or Y₂O₃: 1~ 6%, and/or ZnO:16~23%, and/or WO₃: 5~12%, and/or Nb₂O₅: 2.5~8%, and/or ZrO₂: 1.5~5%, And/or TiO₂: 0~3%, and/or Al₂O₃: 0~3%, and/or Ta₂O₅: 0~3%, and/or P₂O₅: 0~3%, and/or Yb₂O₃: 0~2%, and/or RO:0~5%, and/or Rn₂O:0~3%, and/or clarifying agent: 0~0.1%, wherein RO be MgO, One of CaO, SrO and BaO or a variety of, Rn₂O is Li₂O、Na₂O and K₂One of O or a variety of, clarifying agent Sb₂O₃、 SnO₂, SnO and CeO₂One of or it is a variety of.

(9) according to any optical glass in (1)~(4), component indicates by weight percentage, meets 7 kinds following One of situation or more than one:

1)WO₃/ ZnO is 0.2~1.0；

2)WO₃/Nb₂O₅It is 0.8~10；

3)ZnO/La₂O₃It is 0.3~1.0；

4)ZnO/B₂O₃It is 0.6~2.0；

5)WO₃/(SiO₂+B₂O₃) it is 0.13~0.8；

6)Nb₂O₅+TiO₂+WO₃: 7~30%；

7)La₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) it is 0.6~1.0.

(10) according to any optical glass in (1)~(4), component indicates by weight percentage, meets 7 kinds following One of situation or more than one:

1)WO₃/ ZnO is 0.25~0.75；

2)WO₃/Nb₂O₅It is 1.0~6.0；

3)ZnO/La₂O₃It is 0.4~0.8；

4)ZnO/B₂O₃It is 0.75~1.5；

5)WO₃/(SiO₂+B₂O₃) it is 0.15~0.5；

6)Nb₂O₅+TiO₂+WO₃: 8~20%；

7)La₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) it is 0.75~1.0.

(11) according to any optical glass in (1)~(4), the refractive index (nd) of the optical glass is 1.75~ 1.85, preferably 1.77~1.83, more preferably 1.78~1.82；Abbe number (ν_d) it is 37~47, preferably 38~45, it is more excellent It is selected as 39~44.

(12) according to any optical glass in (1)~(4), the refractive index temperature system of 40~60 DEG C of the optical glass Number (dn/dt) is 7.0 × 10^-6/ DEG C or more, preferably 8.0 × 10^-6/ DEG C or more, more preferably 9.0 × 10^-6/ DEG C or more, into One step is preferably 9.5 × 10^-6/ DEG C or more.

(13) according to any optical glass in (1)~(4), the water-fast effect stability (D of the optical glass_W) be It is more than 2 classes, preferably 1 class；And/or bubble degree is B grades or more, preferably A grades or more, more preferably A₀Grade or more, further Preferably A₀₀Grade；And/or crystallization ceiling temperature be 1150 DEG C hereinafter, preferably 1100 DEG C hereinafter, more preferably 1050 DEG C or less； And/or transition temperature (T_g) be 620 DEG C hereinafter, preferably 615 DEG C hereinafter, more preferably 610 DEG C or less；And/or λ₈₀Be less than or Equal to 410nm, preferably λ₈₀Less than or equal to 405nm, more preferable λ₈₀Less than or equal to 400nm；And/or λ₅It is less than or equal to 350nm, preferably λ₅Less than or equal to 345nm, more preferable λ₅Less than or equal to 342nm.

The present invention also provides a kind of gas preforms:

(14) gas preform is made of any optical glass in (1)~(13).

The present invention also provides a kind of optical elements:

(15) optical element is made of any optical glass in (1)~(13), or using glass described in (14) Prefabricated component is made.

The present invention also provides a kind of optical instruments:

(16) optical instrument containing any optical glass in (1)~(13), or contains the member of optics described in (15) Part.

Beneficial effects of the present invention: the present invention is designed by reasonable component, is obtaining desired refractive index and Abbe number Etc. in the case where optical properties, enable the optical glass obtained that there is larger positive refracting power temperature coefficient and excellent devitrification resistance.

Specific embodiment

In the following, the embodiment of optical glass of the invention is described in detail, but the present invention is not limited to following realities Mode is applied, change appropriate can be carried out in the range of the object of the invention to be implemented.In addition, about repetitive specification, Although there is the case where omitting the description appropriate, but not therefore limit the purport invented.Sometimes this is sent out in the following contents Bright optical glass is referred to as glass.

[optical glass]

The each component range of optical glass of the present invention is illustrated below.In the present specification, if without special theory Bright, the content of each component is all using the weight percent table of the glass substance total amount relative to the composition for being converted into oxide Show.Herein, described " composition for being converted into oxide " refers to, as optical glass constituent of the invention raw material and make In the case that oxide, complex salt and hydroxide etc. decompose when melting and are changed into oxide, by the object of the oxide Matter total amount is as 100%.

Unless in particular situations it is further noted that numberical range listed herein includes upper and lower bound value, " more than " " following " includes endpoint value, and including all integers and score in the range, and is not limited to limited range when institute The occurrence of column.Herein referred "and/or" is inclusive, such as " A and/or B ", refers to only A, or only B, Huo Zhetong When have A and B.

<necessary component and optional components>

B₂O₃It is to form the indispensable necessary component of glass of the present invention, passes through the B containing 10% or more₂O₃, glass can be improved The devitrification resistance of glass, promotion form stable glass；But work as B₂O₃Content is more than 30%, and the refractive index of glass reduces, and glass Chemical stability decline, therefore B in the present invention₂O₃Content is 10~30%, preferably 12~25%, more preferably 15~21%.

SiO₂Have the function of improving the thermal stability of glass, the viscosity side suitable for forming is obtained when shaping to glass solution Face is also that effectively, when its content is more than 20%, the melting behaviour of glass deteriorates, and transition temperature increases, therefore in the present invention Introduce 0~20% SiO₂, in some embodiments, by the SiO for introducing 3% or more₂, the devitrification resistance of glass can be improved And chemical durability, therefore be preferably introduced into the present invention 3~15% SiO₂, further preferably introduce 5~12% SiO₂。

Inventor is had found by lot of experiments, in optical glass of the present invention, B₂O₃Content is greater than SiO₂When content, The chemical stability and devitrification resistance energy of glass, therefore in some embodiments, it is preferred B can be improved₂O₃Content is greater than SiO₂Contain Amount.

La₂O₃Have the function of improving refractive index and maintain low dispersion, if its content is lower than 20%, is difficult to reach State effect；When its content is more than 50%, then the thermal stability of glass declines, and glass transition temperature has the tendency that rising.The present invention In, La₂O₃Content control in the range of 20~50%, preferably 25~45%, more preferably 30~42%.

Gd₂O₃Have the function of improving refractive index, but when its content is more than 15%, the devitrification resistance of glass reduces, transformation Temperature has the tendency that rising, therefore Gd in the present invention₂O₃Content be 15% hereinafter, preferably 0~10%, more preferably 0~ 5%.

Y₂O₃The refractive index that glass is improved while maintaining low dispersibility, if its content is more than 15%, the heat of glass is steady Qualitative and chemical stability reduces, therefore Y in the present invention₂O₃Content be 15% or less.In some embodiments, by drawing Enter 0.5% or more Y₂O₃, the striped degree of glass can be optimized while maintaining glass refraction, therefore in the present invention preferably Y₂O₃Content be 0.5~10%, more preferably 1~6%.

By introducing 10% Yb below in the present invention₂O₃, readily available desired Glass optical constant maintains simultaneously The devitrification resistance of glass, preferably Yb₂O₃Content be 0~5%, more preferably 0~2%, do not introduce further preferably.

Inventor has found that in lanthanide optical glass, La₂O₃、Gd₂O₃、Y₂O₃Introducing ratio will affect glass The devitrification resistance energy and degree of staining of glass further work as La₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) value in 0.5~1.0 range When, while obtaining desired refractive index and Abbe number, the devitrification resistance of glass can get a promotion glass with degree of staining, preferably La₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) value be 0.6~1.0, more preferable La₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) value be 0.75~ 1.0 further preferred La₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) value be 0.8~1.0.

ZnO have the effect of reduce glass transformation temperature and improve chemical stability, the present invention in by introduce 12% with On ZnO, the thermal refractive index coefficient of glass can be improved while sufficiently obtaining the above effect；But when the content of ZnO is more than 30%, the devitrification resistance of glass can reduce.Therefore, the content of ZnO is 12~30%, preferably 15~25% in the present invention, more Preferably 16~23%.

In some embodiments, ZnO and La₂O₃Introducing ratio will affect the transition temperature and bubble degree of glass, into one Step, work as ZnO/La₂O₃When below 0.25, the transition temperature of glass is increased, and bubble degree reduces；Work as ZnO/La₂O₃It is 1.3 When above, the optical constant of glass is difficult to control desired extent, therefore ZnO/La in the present invention₂O₃Range is 0.25~1.3, It is preferred that ZnO/La₂O₃When range is 0.3~1.0, the bubble degree of glass is easier to reach A₀Grade or more, more preferable ZnO/La₂O₃Range It is 0.4~0.8.

In some embodiments, as ZnO and B₂O₃Content ratio ZnO/B₂O₃When below 0.45, the chemistry of glass Stability reduces, and works as ZnO/B₂O₃At 2.75 or more, glass is at glass stability degradation, and meltbility is deteriorated, the decline of striped degree. Therefore, ZnO/B₂O₃Range be 0.45~2.75, preferably 0.6~2.0, more preferably 0.75~1.5.

WO₃It is effective for adjusting optical constant and improving devitrification resistance, and the refractive index temperature system of glass can be improved Number cannot sufficiently obtain said effect if its content is lower than 4%.In some embodiments, WO₃Ingredient is 5% or more When, it can reduce thermal expansion coefficient, having prevents the glass in the manufacturing procedure in accurate pressurization etc. along with temperature change broken The effect split.Work as WO₃Content is more than 20%, and translucency of the glass in the short wavelength region of visible light region deteriorates, glass Color trend increases.Therefore, WO in the present invention₃Content be 4~20%, preferably 5~15%, more preferably 5~12%.

In the present invention, work as WO₃With the introducing ratio WO of the content of ZnO₃When/ZnO is higher than 1.5, the degree of staining of glass has bad The trend of change；Work as WO₃When/ZnO is lower than 0.15, the bubble degree decline of glass further, works as WO₃/ ZnO is in 0.15~1.5 model When enclosing interior, it can also be easier to obtain desired thermal refractive index coefficient.Therefore WO in the present invention₃/ ZnO is 0.15~1.5, preferably 0.2~1.0, more preferably 0.25~0.75.

WO₃Introduction volume and skeleton component SiO₂And B₂O₃Thermal refractive index coefficient, chemical stabilization of the introduction volume to glass Property and devitrification resistance can have an impact, and further, work as WO₃/(SiO₂+B₂O₃) be lower than 0.1 when, the thermal refractive index coefficient of glass It reduces；Work as WO₃/(SiO₂+B₂O₃) be higher than 1.0 when, the chemical stability and devitrification resistance of glass can deteriorate, therefore in the present invention WO₃/(SiO₂+B₂O₃) range be 0.1~1.0, preferably 0.13~0.8, more preferably 0.15~0.5.

Nb₂O₅It is the devitrification resistance for improving glass, chemical durability, refractive index and the component for reducing Abbe number.When it contains Amount is more than 15%, and the thermal stability of glass declines, and liquidus temperature has the tendency that rising, therefore Nb in the present invention₂O₅Content be 15% or less.In some embodiments, by containing 1% or more Nb₂O₅, it can be easy to get high refractive index temperature coefficient, and It is readily able to obtain lower thermal expansion coefficient, have in the manufacturing procedure prevented in accurate pressurization etc. along with temperature change The effect of glass rupture, preferably Nb₂O₅Content is 1~10%, more preferably 2.5~8%.

Preferably work as WO in the present invention₃/Nb₂O₅When being 0.5 or more, glass is easier to obtain desired high refractive index temperature coefficient, And the degree of staining and devitrification resistance of glass can be good, more preferable WO₃/Nb₂O₅It is 0.8~10, further preferably 1.0~6.0.

A small amount of ZrO₂It is added in glass the devitrification resistance energy and chemical stability that can promote glass, while being added properly Measure ZrO₂Erosion of the glass metal to refractory material in production process can be significantly reduced, and improve the refractive index temperature system of glass Number.But if ZrO₂Content is more than 10%, and glass becomes difficult to melt, devitrification resistance can rapid decrease, therefore, the present invention Middle ZrO₂Content is limited to 10% hereinafter, preferably 1~8%, and more preferably 1.5~5%.

TiO₂Have the function of improving glass refraction, and glass network can be participated in and formed, appropriate introduce makes glass more Stablize, but glass dispersion can dramatically increase after introducing, while the decrease in transmission of the shortwave part of glass visible light region, glass The tendency of coloring increases.Therefore, TiO of the present invention₂Content be 0~10%, preferably 0~8%, more preferably 0~3%.

Nb₂O₅、TiO₂And WO₃It is effectively, when it adds up to content Nb to the refractive index and dispersion that improve optical glass₂O₅+ TiO₂+WO₃When lower than 5%, glass is difficult to obtain desired refractive index and high refractive index temperature coefficient, works as Nb₂O₅+TiO₂+WO₃It is high When 40%, the refractive index of glass exceeds design requirement, and degree of staining and devitrification resistance can deteriorate.Therefore, Nb in the present invention₂O₅+ TiO₂+WO₃It is limited to 5~40%, preferably 7~30%, more preferably 8~20%

Rn₂O(Rn₂O is Li₂O、Na₂O or K₂One of O or a variety of) meltbility of glass can be improved, reduce vitrifying Transition temperature, when its content is more than 10%, stability, glass is deteriorated, and refractive index and thermal refractive index coefficient are greatly reduced, because This Rn of the present invention₂O content is 0~10%, preferably 0~5%, more preferably 0~3%, is not introduced further preferably.

RO (one of RO BaO, SrO, CaO or MgO or a variety of) can improve the meltbility of glass, reduce vitrifying Transition temperature, but when its content is more than 20%, the devitrification resistance of glass reduces, thermal refractive index coefficient decline.Therefore, this hair Bright RO content is 0~20%, preferably 0~10%, more preferably 0~5%.

Ta₂O₅Have the function of improving refractive index, promote glass devitrification resistance energy, but compared with other compositions, Ta₂O₅'s Price is very expensive, from the point of view of practical and cost, should reduce its usage amount to the greatest extent.Therefore, Ta of the invention₂O₅Contain Amount is limited to 0~10%, preferably 0~5%, more preferably 0~3%.

It is a small amount of to introduce Al₂O₃It can improve and form the stability and chemical stability of glass, but when its content is more than 8%, show The tendency that glass melting is deteriorated, devitrification resistance reduces, therefore Al of the present invention₂O₃Content be 0~8%, preferably 0~5%, More preferably 0~3%.

P₂O₅It is the optional member that the devitrification resistance of glass can be improved, especially by making P₂O₅Content be 10% with Under, it can inhibit the reduction of the chemical durability especially water resistance of glass.Therefore, P₂O₅Content is limited to 10% hereinafter, preferably 5% hereinafter, more preferable 3% hereinafter, do not introduce further preferably.

By the Sb for being added 0~1%₂O₃、SnO₂, SnO and CeO₂One of or various ingredients as clarifying agent, can be with Improve the clarifying effect of glass.But the present invention is due to having reasonable formula design, itself clarifying effect is preferable, and bubble degree is excellent It is different, thus be preferably added to 0~0.5% clarifying agent, more preferably be added 0~0.1% clarifying agent, do not introduce further preferably clear Clear agent.

F can reduce glass dispersion, promote glass transmitance, improve glass devitrification resistance energy, but it is in melting and molding The volatilization of process can make the data fluctuations of glass become larger, while the volatilization of F will lead to the generation of striped in forming process.Separately Outside, the volatilization of F can generate potential security threat to human body and environment.F content is limited within 5% in the present invention, preferably Not introduce.

<component that should not contain>

In glass of the present invention, the oxide of the transition metal such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo, even if individually Or in the case that compound ground contains on a small quantity, glass is also subject to coloration, the specific wavelength in visible light region generates absorption, thus The property for weakening raising visible light transmittance effect of the invention, therefore it is desirable, especially for the transmitance of visible light region wavelength The optical glass required, does not preferably contain actually.

The oxide of Th, Cd, Tl, Os, Be and Se have what control used to incline as harmful chemical substance in recent years To being to the measure of environmental protection in the manufacturing process of glass, the disposition after manufacturing procedure and commercialization not only must It needs.Therefore, it in the case where paying attention to the influence to environment, other than being inevitably mixed into, does not preferably contain actually They.Optical glass becomes the substance for not including pollution environment actually as a result,.Therefore, even if not taking special environment pair Measure in plan, optical glass of the invention are also able to carry out manufacture, processing and discard.

Environmental-friendly in order to realize, optical glass of the invention does not contain As₂O₃And PbO.Although As₂O₃With elimination gas Bubble and the effect for preferably preventing glass coloration, but As₂O₃Addition can increase glass smelting furnace is especially to the platinum of platinum smelting furnace Gold corrodes, and causes more platinum ions to enter glass, adversely affects to the service life of platinum smelting furnace.PbO can be significant The high refractive index of raising glass and high dispersion, but PbO and As₂O₃All cause the substance of environmental pollution.

" not introducing " " not containing " " 0% " described herein refers to not deliberately by the compound, molecule or element etc. It is added in optical glass of the present invention as raw material；But as the raw material and/or equipment of production optical glass, can exist certain It is not the impurity deliberately added or component, a small amount of or trace can contains in final optical glass, such situation is also in this hair In the protection scope of bright patent.

In the following, being illustrated to the performance of optical glass of the invention.

<refractive index and Abbe number>

Optical glass refractive index (nd) and Abbe number (ν_d) tested according to method as defined in GB/T 7962.1-2010.

The refractive index (nd) of optical glass of the present invention is 1.75~1.85, preferably 1.77~1.83, more preferably 1.78 ~1.82；Abbe number (ν_d) it is 37~47, preferably 38~45, more preferably 39~44.

<water-fast effect stability>

Optical glass is water-fast effect stability (D_W) (powder method) according to method as defined in GB/T 17129 test.

The water-fast effect stability (D of optical glass of the present invention_W) it is 2 classes or more, preferably 1 class.

<bubble degree>

The bubble degree of optical glass is by the test of method as defined in GB/T7962.8-2010.

Optical glass bubble degree of the present invention is B grades or more, preferably A grades or more, more preferably A₀Grade or more, it is further excellent It is selected as A₀₀Grade.

<crystallization ceiling temperature>

Using the crystallization property of temperature gradient furnace method measurement glass, glass is made to the sample of 180*10*10mm, side polishes, It is put into the furnace with temperature gradient (5 DEG C/cm) to take out after being warming up to 1400 DEG C of heat preservations 4 hours and naturally cools to room temperature, aobvious There is the crystallization ceiling temperature that the corresponding maximum temperature of crystal is glass in micro- microscopic observation devitrification of glass situation, glass.

The crystallization ceiling temperature of optical glass of the invention is for 1150 DEG C hereinafter, preferably 1100 DEG C hereinafter, more preferably 1050 DEG C or less.

<thermal refractive index coefficient>

According to 7962.4-2010 prescriptive procedure of GB/T, the refractive index temperature in 40~60 DEG C of range of optical glass is tested Coefficient (d line dn/dt relative (10^-6/℃))

Temperature coefficient of optical glass refractive index (dn/dt) of the present invention is 7.0 × 10^-6/ DEG C or more, preferably 8.0 × 10^-6/ DEG C or more, more preferably 9.0 × 10^-6/ DEG C or more, further preferably 9.5 × 10^-6/ DEG C or more.

<transition temperature>

Transition temperature (the T of glass_g) tested by method as defined in GB/T7962.16-2010.

Transition temperature (the T of optical glass of the invention_g) be 620 DEG C hereinafter, preferably 615 DEG C hereinafter, more preferably 610 DEG C or less.

<degree of staining>

The shortwave transmitted spectrum characteristic degree of staining (λ of glass of the present invention₈₀/λ₅) indicate.λ₈₀Refer to that glass transmittance reaches Corresponding wavelength, λ when 80%₅Refer to that glass transmittance reaches corresponding wavelength when 5%.Wherein, λ₈₀Measurement be using having The glass with a thickness of 10 ± 0.1mm of two parallel to each other and optical polish opposite planes, measures from 280nm to 700nm Spectral transmission in wavelength domain and the wavelength for showing transmissivity 80%.So-called spectral transmission or transmissivity are to glass Above-mentioned surface vertically incident intensity I_inLight, project intensity I through glass and from plane_outLight in the case where lead to Cross I_out/I_inThe amount of expression, and also contain the transmissivity of the surface reflection loss on the above-mentioned surface of glass.The folding of glass It is higher to penetrate rate, surface reflection loss is bigger.Therefore, in glass of high refractive index, λ₈₀The small coloring for meaning glass itself of value Seldom.

Optical glass λ of the invention₈₀Range be less than or equal to 410nm, preferably λ₈₀Range be less than or equal to 405nm, more preferable λ₈₀Range be less than or equal to 400nm.λ₅Range be less than or equal to 350nm, preferably λ₅Range For less than or equal to 345nm, more preferable λ₅Range be less than or equal to 342nm.

[manufacturing method]

The manufacturing method of optical glass of the present invention is as follows: glass of the invention is produced using conventional raw material and common process, It the use of carbonate, nitrate, sulfate, hydroxide, oxide etc. is raw material, according to a conventional method after ingredient, the furnace that will prepare Material is put into 1300~1400 DEG C of smelting furnace and is melted, and after clarified, stirring and homogenizing, obtains no bubble and be free of The homogeneous melt glass of undissolved substance casting mold and anneals this melten glass in mold.Those skilled in the art's energy Enough according to actual needs, raw material, process and technological parameter are properly selected.

[gas preform and optical element]

Molded such as the means of attrition process or reheating, compression molding precise punch forming means can be used, Gas preform is made by made optical glass.I.e., it is possible to mechanical by being ground and being ground to optical glass etc. Processing makes gas preform, or by the preform for making compression molding by optical glass, to the preform Carry out carrying out attrition process again after reheating is molded to make gas preform, or and to attrition process is carried out it is manufactured pre- Precise punch forming is carried out at parison to make gas preform.

It should be noted that the means for preparing gas preform are not limited to above-mentioned means.As described above, optics of the invention Glass is useful for various optical elements and optical design, wherein particularly preferably by optical glass of the invention formed it is pre- at Parison carries out molded, precise punch forming of reheating etc., the optical elements such as production lens, prism using the preform.

Gas preform and optical element of the invention is formed by the optical glass of aforementioned present invention.Glass of the invention Prefabricated component has excellent characteristics possessed by optical glass；Optical element of the invention has excellent spy possessed by optical glass Property, it is capable of providing the optical elements such as the costly various lens of optics, prism.

As the example of lens, can enumerate lens face be spherical surface or aspherical recessed meniscus shaped lens, male bend moon-shaped lens, The various lens such as biconvex lens, biconcave lens, plano-convex lens, plano-concave lens.

[optical instrument]

Optical glass of the present invention is formed by optical element and can make such as camera installation, picture pick-up device, display equipment and prison Control the optical instruments such as equipment.

Embodiment

<optical glass embodiment>

In order to further clearly illustrate and illustrate technical solution of the present invention, non-limiting embodiment below is provided.

The present embodiment obtains the optics glass with composition shown in 1~table of table 2 using the manufacturing method of above-mentioned optical glass Glass.In addition, the test method measures the characteristic of each glass through the invention, and measurement result is indicated in 1~table of table 2 In.

Table 1

Table 2

<gas preform embodiment>

The means of the obtained glass of optical glass Examples 1 to 20 use such as attrition process or reheating are molded, The means of the compression moldings such as precise punch forming, it is saturating to make recessed meniscus shaped lens, male bend moon-shaped lens, biconvex lens, concave-concave The prefabricated component of the various lens such as mirror, plano-convex lens, plano-concave lens, prism etc..

<optical element embodiment>

By obtained these prefabricated components annealing of above-mentioned optical precast product embodiment, the same of the deformation of inside glass is being reduced When be finely adjusted so that the optical characteristics such as refractive index reach desirable value.

Then, each prefabricated component is ground, ground, make recessed meniscus shaped lens, male bend moon-shaped lens, biconvex lens, The various lens such as biconcave lens, plano-convex lens, plano-concave lens, prism.It can also Tu Bufang on the surface of obtained optical element Reflectance coating.

<optical instrument embodiment>

By optical element made from above-mentioned optical element embodiment by optical design, by using one or more optics Element forms optical component or optical module, can be used for such as imaging device, sensor, microscope, medical science, number and throws Shadow, communication, optical communication technique/information transmission, optics/illumination in automotive field, photoetching technique, excimer laser, crystalline substance Piece, computer chip and integrated circuit and electronic device including such circuit and chip, or taking the photograph for automotive field As equipment and device.

Claims (16)

1. optical glass, which is characterized in that its component indicates by weight percentage, contains: 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%, wherein WO₃/ ZnO is 0.15~1.5.

2. optical glass according to claim 1, which is characterized in that its component indicates by weight percentage, also contains: TiO₂: 0~10%, and/or Al₂O₃: 0~8%, and/or Ta₂O₅: 0~10%, and/or P₂O₅: 0~10%, and/or Yb₂O₃: 0 ~10%, and/or RO:0~20%, and/or Rn₂O:0~10%, and/or clarifying agent: 0~1%, wherein RO be MgO, CaO, One of SrO and BaO or a variety of, Rn₂O is Li₂O、Na₂O and K₂One of O or a variety of, clarifying agent Sb₂O₃、SnO₂、 SnO and CeO₂One of or it is a variety of.

3. optical glass, which is characterized in that its component indicates by weight percentage, by 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%, clarifying agent: 0~1% forms, wherein WO₃/ ZnO be 0.15~1.5, RO MgO, One of CaO, SrO and BaO or a variety of, Rn₂O is Li₂O、Na₂O and K₂One of O or a variety of, clarifying agent Sb₂O₃、 SnO₂, SnO and CeO₂One of or it is a variety of.

4. optical glass, which is characterized in that its component indicates by weight percentage, contains SiO₂And B₂O₃, and B₂O₃Content is greater than SiO₂Content；Contain WO₃、Nb₂O₅And ZnO, wherein WO₃/ ZnO is 0.15~1.5, WO₃/Nb₂O₅It is 0.5 or more；The optics The refractive index nd of glass is 1.75~1.85, and Abbe number vd is 37~47.

5. optical glass described in any claim according to claim 1~4, which is characterized in that its component percentage by weight Than indicating, in which: SiO₂: 3~15%, and/or B₂O₃: 12~25%, and/or La₂O₃: 25~45%, and/or Gd₂O₃: 0~ 10%, and/or Y₂O₃: 0.5~10%, and/or ZnO:15~25%, and/or WO₃: 5~15%, and/or Nb₂O₅: 1~10%, And/or ZrO₂: 1~8%, and/or TiO₂: 0~8%, and/or Al₂O₃: 0~5%, and/or Ta₂O₅: 0~5%, and/or P₂O₅: 0~5%, and/or Yb₂O₃: 0~5%, and/or RO:0~10%, and/or Rn₂O:0~5%, and/or clarifying agent: 0~ 0.5%, wherein RO is one of MgO, CaO, SrO and BaO or a variety of, Rn₂O is Li₂O、Na₂O and K₂One of O or more Kind, clarifying agent Sb₂O₃、SnO₂, SnO and CeO₂One of or it is a variety of.

6. optical glass described in any claim according to claim 1~3, which is characterized in that its component percentage by weight Than indicating, in which: B₂O₃Content is greater than SiO₂Content；And/or WO₃/Nb₂O₅It is 0.5 or more.

7. optical glass described in any claim according to claim 1~4, which is characterized in that its component percentage by weight Than indicating, meet one of following 5 kinds of situations or more than one:

1)ZnO/La₂O₃It is 0.25~1.3；

2)ZnO/B₂O₃It is 0.45~2.75；

3)WO₃/(SiO₂+B₂O₃) it is 0.1~1.0；

4)Nb₂O₅+TiO₂+WO₃: 5~40%；

5)La₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) it is 0.5~1.0.

8. optical glass described in any claim according to claim 1~4, which is characterized in that its component percentage by weight Than indicating, in which: SiO₂: 5~12%, and/or B₂O₃: 15~21%, and/or La₂O₃: 30~42%, and/or Gd₂O₃: 0~ 5%, and/or Y₂O₃: 1~6%, and/or ZnO:16~23%, and/or WO₃: 5~12%, and/or Nb₂O₅: 2.5~8% and/ Or ZrO₂: 1.5~5%, and/or TiO₂: 0~3%, and/or Al₂O₃: 0~3%, and/or Ta₂O₅: 0~3%, and/or P₂O₅: 0 ~3%, and/or Yb₂O₃: 0~2%, and/or RO:0~5%, and/or Rn₂O:0~3%, and/or clarifying agent: 0~0.1%, Wherein RO is one of MgO, CaO, SrO and BaO or a variety of, Rn₂O is Li₂O、Na₂O and K₂One of O or a variety of, clarification Agent is Sb₂O₃、SnO₂, SnO and CeO₂One of or it is a variety of.

9. optical glass described in any claim according to claim 1~4, which is characterized in that its component percentage by weight Than indicating, meet one of following 7 kinds of situations or more than one:

1)WO₃/ ZnO is 0.2~1.0；

2)WO₃/Nb₂O₅It is 0.8~10；

3)ZnO/La₂O₃It is 0.3~1.0；

4)ZnO/B₂O₃It is 0.6~2.0；

5)WO₃/(SiO₂+B₂O₃) it is 0.13~0.8；

6)Nb₂O₅+TiO₂+WO₃: 7~30%；

7)La₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) it is 0.6~1.0.

10. optical glass described in any claim according to claim 1~4, which is characterized in that its component percentage by weight Than indicating, meet one of following 7 kinds of situations or more than one:

1)WO₃/ ZnO is 0.25~0.75；

2)WO₃/Nb₂O₅It is 1.0~6.0；

3)ZnO/La₂O₃It is 0.4~0.8；

4)ZnO/B₂O₃It is 0.75~1.5；

5)WO₃/(SiO₂+B₂O₃) it is 0.15~0.5；

6)Nb₂O₅+TiO₂+WO₃: 8~20%；

7)La₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) it is 0.75~1.0.

11. optical glass described in any claim according to claim 1~4, which is characterized in that the folding of the optical glass Penetrating rate nd is 1.75~1.85, preferably 1.77~1.83, more preferably 1.78~1.82；Abbe number ν d is 37~47, preferably It is 38~45, more preferably 39~44.

12. optical glass described in any claim according to claim 1~4, which is characterized in that the optical glass 40~ 60 DEG C of thermal refractive index coefficient dn/dt is 7.0 × 10^-6/ DEG C or more, preferably 8.0 × 10^-6/ DEG C or more, more preferably 9.0 ×10^-6/ DEG C or more, further preferably 9.5 × 10^-6/ DEG C or more.

13. optical glass described in any claim according to claim 1~4, which is characterized in that the optical glass it is resistance to Water acts on stability D_WMore than 2 classes, preferably 1 class；And/or bubble degree be B grades or more, preferably A grades or more, more preferably A₀Grade or more, further preferably A₀₀Grade；And/or crystallization ceiling temperature be 1150 DEG C hereinafter, preferably 1100 DEG C hereinafter, more excellent It is selected as 1050 DEG C or less；And/or transition temperature T_gFor 620 DEG C hereinafter, preferably 615 DEG C hereinafter, more preferably 610 DEG C or less； And/or λ₈₀Less than or equal to 410nm, preferably λ₈₀Less than or equal to 405nm, more preferable λ₈₀Less than or equal to 400nm；And/or λ₅ Less than or equal to 350nm, preferably λ₅Less than or equal to 345nm, more preferable λ₅Less than or equal to 342nm.

14. gas preform is made of optical glass described in claim 1~13 any claim.

15. optical element is made of optical glass described in claim 1~13 any claim, or is wanted using right Gas preform described in asking 14 is made.

16. optical instrument containing optical glass described in claim 1~13 any claim, or contains claim 15 The optical element.