CN110028239A

CN110028239A - Optical glass, gas preform, optical element and optical instrument

Info

Publication number: CN110028239A
Application number: CN201910433655.0A
Authority: CN
Inventors: 孙伟
Original assignee: Chengdu Guangming Optoelectronics Co Ltd
Current assignee: Chengdu Guangming Optoelectronics Co Ltd
Priority date: 2019-05-23
Filing date: 2019-05-23
Publication date: 2019-07-19
Anticipated expiration: 2039-05-23
Also published as: CN110028239B

Abstract

The present invention provides a kind of Spectralite with high refractivity and low dispersion, and component in terms of weight percentage, contains: La₂O₃: 15~40%；Gd₂O₃: 10~30%；WO₃: 10~30%；TiO₂: 0~10%；ZrO₂: 0~10%, wherein (Gd₂O₃+WO₃)/(La₂O₃+TiO₂+ZrO₂) it is 0.6~2.5.The present invention adjusts the proportion between constituent content by rationally introducing various components, and for the optical glass that the present invention obtains with desired refractive index and while dispersion, chemical stability is excellent.

Description

Optical glass, gas preform, optical element and optical instrument

Technical field

The present invention relates to a kind of optical glass, pre- more particularly, to optical glass, the glass of a kind of high-refractivity and low-dispersion Product, optical element and optical instrument.

Background technique

High-refractivity and low-dispersion glass formed lens can be combined with the lens etc. formed by ultra-low dispersion glass and Cemented lens is made, so as to correcting chromatic aberration and makes optical system densification.Therefore, high-refractivity and low-dispersion glass As the optical element for constituting the projection optical systems such as imaging optical system, projector, in occupation of very important position.

In recent years, optical glass is widely applied in the fields such as vehicle-mounted, monitoring security protection, and is applied to the fields such as vehicle-mounted, security protection Optical glass is also higher to the chemical stability requirements such as acidproof, water-fast of optical glass due to being chronically exposed to outdoor.Separately On the one hand, optical glass in process, can also contact a large amount of corrosive medium, if its is acidproof, water resistance is poor, it will shadow The image quality of optical glass is rung, or even keeps the optical element of processing completely discarded.Therefore, field of photovoltaic materials is to excellent The demand of the Spectralite with high refractivity and low dispersion of chemical stability is more urgent.

Summary of the invention

Technical problem to be solved by the invention is to provide a kind of high-refractivity and low-dispersions with superior chemical stability Optical glass.

The present invention solve technical problem the technical solution adopted is that:

(1) optical glass, component indicate by weight percentage, contain: La₂O₃: 15~40%；Gd₂O₃: 10~30%； WO₃: 10~30%；TiO₂: 0~10%；ZrO₂: 0~10%, wherein (Gd₂O₃+WO₃)/(La₂O₃+TiO₂+ZrO₂) be 0.6~ 2.5。

(2) optical glass according to (1), component indicates by weight percentage, also contains: B₂O₃: 5~20%； SiO₂: 0~10%；Y₂O₃: 0~10%；Yb₂O₃: 0~8%；Ta₂O₅: 0~10%；Nb₂O₅: 0~10%；ZnO:0~10%； Al₂O₃: 0~5%；RO:0~10%；Rn₂O:0~5%, wherein RO is one of MgO, CaO, SrO, BaO or a variety of, Rn₂O For Li₂O、Na₂O、K₂One of O or a variety of.

(3) optical glass, component indicate by weight percentage, contain: B₂O₃: 5~20%；SiO₂: 0~10%； La₂O₃: 15~40%；Gd₂O₃: 10~30%；WO₃: 10~30%；ZrO₂: 0~10%；Nb₂O₅: 0~10%.

(4) optical glass according to (3), component indicates by weight percentage, also contains: Y₂O₃: 0~10%； And/or Yb₂O₃: 0~8%；And/or Ta₂O₅: 0~10%；And/or ZnO:0~10%；And/or TiO₂: 0~10%；And/or Al₂O₃: 0~5%；And/or RO:0~10%；And/or Rn₂O:0~5%, wherein RO is one of MgO, CaO, SrO, BaO Or a variety of, Rn₂O is Li₂O、Na₂O、K₂One of O or a variety of.

(5) according to any optical glass in (1)~(4), component indicates by weight percentage, (Gd₂O₃+WO₃)/ (La₂O₃+TiO₂+ZrO₂) it is 0.6~2.5, preferably (Gd₂O₃+WO₃)/(La₂O₃+TiO₂+ZrO₂) it is 0.7~2.0, more preferably (Gd₂O₃+WO₃)/(La₂O₃+TiO₂+ZrO₂) it is 0.8~1.8, further preferred (Gd₂O₃+WO₃)/(La₂O₃+TiO₂+ZrO₂) be 1.0~1.5.

(6) according to any optical glass in (1)~(4), component indicates by weight percentage, Gd₂O₃/(La₂O₃+ Gd₂O₃+Y₂O₃) it is 0.15~0.7, preferably Gd₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) it is 0.2~0.6, more preferable Gd₂O₃/(La₂O₃+ Gd₂O₃+Y₂O₃) it is 0.3~0.55.

(7) according to any optical glass in (1)~(4), component indicates by weight percentage, 3 × SiO₂/WO₃For 0.05~1.5, preferably 3 × SiO₂/WO₃It is 0.1~1.0, more preferable 3 × SiO₂/WO₃It is 0.2~0.8.

(8) according to any optical glass in (1)~(4), component indicates by weight percentage, B₂O₃/WO₃It is 0.2 ~1.5, preferably B₂O₃/WO₃It is 0.3~1.0, more preferable B₂O₃/WO₃It is 0.4~0.8.

(9) according to any optical glass in (1)~(4), component indicates by weight percentage, (Gd₂O₃+ La₂O₃)/(WO₃+Nb₂O₅) it is 0.8~3.5, preferably (Gd₂O₃+La₂O₃)/(WO₃+Nb₂O₅) it is 1.0~3.0, more preferable (Gd₂O₃+ La₂O₃)/(WO₃+Nb₂O₅) it is 1.5~2.5.

(10) according to any optical glass in (1)~(4), component indicates by weight percentage, ZnO/Gd₂O₃'s Value is for 0.5 hereinafter, it is preferred that ZnO/Gd₂O₃Value be 0.3 hereinafter, more preferable ZnO/Gd₂O₃Value be 0.2 or less.

(11) according to any optical glass in (1)~(4), component indicates by weight percentage, Nb₂O₅/(Nb₂O₅ +TiO₂+Ta₂O₅) it is 0.3~1.0, preferably Nb₂O₅/(Nb₂O₅+TiO₂+Ta₂O₅) it is 0.4~0.9, more preferable Nb₂O₅/(Nb₂O₅+ TiO₂+Ta₂O₅) it is 0.5~0.8.

(12) according to any optical glass in (1)~(4), component indicates by weight percentage, Ta₂O₅/WO₃For 0.8 hereinafter, it is preferred that Ta₂O₅/WO₃It is 0.02~0.5, more preferable Ta₂O₅/WO₃It is 0.05~0.3.

(13) according to any optical glass in (1)~(4), component indicates by weight percentage, contains: B₂O₃: 8 ~18%；And/or SiO₂: 1~8%；And/or La₂O₃: 21~36%；And/or Gd₂O₃: 13~26%；And/or WO₃: 12~ 26%；And/or ZrO₂: 1~8%；And/or Nb₂O₅: 1~8%；And/or Y₂O₃: 0~5%；And/or Yb₂O₃: 0~5%；With/ Or Ta₂O₅: 0~8%；And/or ZnO:0~8%；And/or TiO₂: 0~5%；And/or Al₂O₃: 0~2%；And/or RO:0~ 5%；And/or Rn₂O:0~2%, wherein RO is one of MgO, CaO, SrO, BaO or a variety of, Rn₂O is Li₂O、Na₂O、K₂O One of or it is a variety of.

(14) according to any optical glass in (1)~(4), component indicates by weight percentage, contains: B₂O₃: 10 ~15%；And/or SiO₂: 1~6%；And/or La₂O₃: 26~35%；And/or Gd₂O₃: 16~25%；And/or WO₃: 15~ 25%；And/or ZrO₂: 2~7%；And/or Nb₂O₅: 2~6%；And/or Y₂O₃: 0~2%；And/or Yb₂O₃: 0~1%；With/ Or Ta₂O₅: 1~6%；And/or ZnO:0~3%；And/or TiO₂: 0~3%；And/or Al₂O₃: 0~1%；And/or RO:0~ 2%；And/or Rn₂O:0~1%, wherein RO is one of MgO, CaO, SrO, BaO or a variety of, Rn₂O is Li₂O、Na₂O、K₂O One of or it is a variety of.

(15) according to any optical glass in (1)~(4), component indicates to contain 0~1% by weight percentage Clarifying agent, the clarifying agent are Sb₂O₃、SnO₂, SnO and CeO₂One of or it is a variety of.

(16) according to any optical glass in (1)~(4), the refractive index nd of the optical glass is 1.88~ 1.95, preferably 1.89~1.94, more preferably 1.90~1.93；Abbe number vd is 31~38, preferably 32~37, more preferably It is 33~36.

(17) according to any optical glass in (1)~(4), the water-fast effect stability D of the optical glass_WIt is 2 It is more than class, preferably 1 class；And/or acidproof effect stability D_AMore than 2 classes, preferably 1 class；And/or thermal expansion coefficient α_{20~120 DEG C}It is 80 × 10^-7/ K is hereinafter, preferably 78 × 10^-7/ K is hereinafter, more preferably 75 × 10^-7/ K or less；And/or Knoop is hard Spend H_KIt is 650 × 10⁷Pa or more, preferably 655 × 10⁷Pa or more, more preferably 660 × 10⁷Pa or more, further preferably 665×10⁷Pa or more.

The present invention also provides a kind of gas preform, optical element and optical instruments.

(18) gas preform is made of any optical glass in (1)~(17).

(19) optical element is made of any optical glass in (1)~(17), or using glass described in (18) Prefabricated component is made.

(20) optical instrument containing any optical glass in (1)~(17), or contains the member of optics described in (19) Part.

The beneficial effects of the present invention are: by reasonably introducing various components, and the proportion between constituent content is adjusted, this While the optical glass that invention obtains has desired refractive index and dispersion, chemical stability is excellent.

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.Glass composition in the present invention and this specification can be for example, by ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) the methods of quantified.Had using the assay value that ICP-AES is found out When can include the evaluated error of assay value ± 5% or so.

SiO₂The viscosity of melten glass can be improved, stable glass is promoted to be formed, by by SiO₂Introduction volume control exist 10% hereinafter, can reduce the partial dispersion of glass than, inhibit the rising of glass transition temperature.Therefore SiO in the present invention₂'s Content is 0~10%, preferably 1~8%.In some embodiments in, by by SiO₂Introduction volume control 6% with Under, it can also reduce the specific gravity of glass, and be easily obtained the target of high refractive index of the present invention, therefore more preferable SiO₂Content be 1~6%.

In the glass containing a large amount of rare earth oxides, B₂O₃It is that indispensable oxide component is formed as glass.This Pass through the B of 5% or more introducing in invention₂O₃, can reduce the specific gravity of glass, and can reduce the devitrification caused by reheating And coloring；If B₂O₃Content be more than 20%, the refractive index of glass reduces, and the chemical stability decline of glass, therefore the present invention Middle B₂O₃Content is 5~20%, preferably 8~18%, more preferably 10~15%.

La₂O₃With improving refractive index and improving the effect of acidproof effect stability, work as La₂O₃Content it is excessive when, glass Thermal stability and devitrification resistance decline.La in the present invention₂O₃Content be 15~40%, preferably 21~36%, more preferably 26~35%.

Gd₂O₃Introducing can be improved the refractive index and chemical stability of glass, by introducing 10% or more in the present invention Gd₂O₃, while obtaining above-mentioned performance, improve the thermal stability and devitrification resistance energy of glass；If Gd₂O₃Content is more than 30%, The specific gravity and cost increase of glass.Therefore Gd in the present invention₂O₃Content be 10~30%, preferably 13~26%, more preferably 16~25%.

Y₂O₃Have the function of improving glass refraction, passes through 10% Y below of introducing in the present invention₂O₃, can maintain While high refractive index, the thermal stability of glass and chemical stability is inhibited to reduce.Therefore, Y in the present invention₂O₃Content be 0~ 10%, preferably 0~5%, more preferably 0~2%, it does not introduce further preferably.

Pass through the relationship between the content of control rare earth oxide component, the devitrification resistance of adjustable glass in the present invention Energy.Especially control Gd₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) in 0.15~0.7 range, obtaining the same of excellent devitrification resistance energy When, the light transmission rate and thermal stability of optical glass are improved, preferably Gd₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) it is 0.2~0.6, More preferable Gd₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) it is 0.3~0.55.

By introducing 8% Yb below in the present invention₂O₃, readily available desired Glass optical constant, while maintaining glass The devitrification resistance of glass, preferably Yb₂O₃Content be 0~5%, more preferably 0~1%.

WO₃It is effectively, by introducing 10% or more in the present invention to the high refractive index and devitrification resistance that obtain glass WO₃, the coloring of the glass as caused by other high refractive index components can be reduced to a certain extent, and improves the melting of glass raw material Property；When its content is more than 30%, the dispersion of glass is difficult to reach design requirement, short wavelength region of the glass in visible light region Translucency deterioration.Therefore, WO in the present invention₃Content be 10~30%, preferably 12~26%, more preferably 15~ 25%.

It is found through inventor's lot of experiments, in some embodiments, by the SiO for introducing 3 parts of contents₂With 1 part The WO of content₃Synergistic effect, and make its relation with contents SiO₂3 times of content and WO₃3 × SiO of ratio of content₂/WO₃0.05 In~1.5 ranges, the devitrification resistance energy of glass can be improved in the case where guaranteeing low thermal coefficient of expansion；It is preferred that 3 × SiO₂/WO₃ Also to can further improve the chemical stability of glass in 0.1~1.0 range.Therefore 3 × SiO₂/WO₃Range be 0.05~ 1.5, preferably 3 × SiO₂/WO₃Range be 0.1~1.0, more preferable 3 × SiO₂/WO₃Range be 0.2~0.8.

In the present invention, if B₂O₃/WO₃0.2 hereinafter, the melting behaviour of glass reduces, if B₂O₃/WO₃More than 1.5, then The devitrification resistance of glass can have the tendency that deterioration, therefore B in the present invention₂O₃/WO₃In 0.2~1.5 range.Further, lead to Crossing makes B₂O₃/WO₃In 0.3~1.0 range, optical glass can also be made to be easier to obtain suitable hardness.Therefore B in the present invention₂O₃/ WO₃It is 0.2~1.5, preferably 0.3~1.0, more preferably 0.4~0.8.

Nb₂O₅It is the component of the devitrification resistance for improving glass, chemical stability and refractive index.When its content is more than 10%, glass The thermal stability decline of glass, liquidus temperature have the tendency that rising, therefore Nb in the present invention₂O₅Content be 10% or less.Some In embodiment, especially containing 1% or more Nb₂O₅, it is readily able to obtain lower thermal expansion coefficient, having prevents in essence The effect along with the glass rupture in the manufacturing procedure of temperature change such as close pressurization, preferably Nb₂O₅Content is 1~8%, more excellent It is selected as 2~6%.

Inventor's lot of experiments discovery, if (Gd₂O₃+La₂O₃)/(WO₃+Nb₂O₅) value less than 0.8, glass is difficult to Low dispersion is obtained, while the light transmission rate of glass and devitrification resistance can reduce；If (Gd₂O₃+La₂O₃)/(WO₃+Nb₂O₅) value More than 3.5, the thermal expansion coefficient of glass rises, and hardness is deteriorated.Therefore (Gd₂O₃+La₂O₃)/(WO₃+Nb₂O₅) value be 0.8~ 3.5, preferably 1.0~3.0, more preferably 1.5~2.5.

ZrO₂The refractive index of glass can be improved in component, by by ZrO₂The content of component is set as 10% hereinafter, being able to maintain that institute Desired dispersion, and can inhibit because of ZrO₂Excess contain the reduction of caused devitrification resistance.ZrO₂Content be 0~10%, Preferably 1~8%, more preferably 2~7%.

TiO₂It can be used for adjusting the refractive index and dispersion of glass, pass through control TiO in the present invention₂Content 10% with Under, it can inhibit chemical stability, light transmission rate and the devitrification resistance of glass that can deteriorate.Therefore, TiO in the present invention₂Content is 0 ~10%, preferably 0~5%, more preferably 0~3%.In some embodiments, even if a small amount of contains TiO₂, can also lead It causes the chemical stability of glass to be deteriorated, therefore does not contain TiO further preferably₂。

It is found through inventor's lot of experiments, if (Gd₂O₃+WO₃)/(La₂O₃+TiO₂+ZrO₂) value less than 0.6, glass The chemical stability of glass is deteriorated, and light transmission rate and hardness reduce；If (Gd₂O₃+WO₃)/(La₂O₃+TiO₂+ZrO₂) value be more than 2.5, glass can be reduced at glass stability and devitrification resistance.Therefore (Gd in the present invention₂O₃+WO₃)/(La₂O₃+TiO₂+ZrO₂) Value be 0.6~2.5, preferably 0.7~2.0, more preferably 0.8~1.8, further preferably 1.0~1.5.

ZnO is any component for the devitrification resistance for reducing the liquidus temperature of glass and improving glass, is had in melting glass The effect for promoting glass raw material melting when glass, is any component in glass of the present invention.From meltbility, the thermostabilization for improving glass Property, the performances such as mouldability, machining property set out, ZnO content is limited to 0~10%, preferably 0~8% in the present invention, more Preferably 0~3%, it does not introduce further preferably.

In some embodiments of optical glass of the present invention, work as ZnO/Gd₂O₃Value 0.5 hereinafter, optical glass can be made to have There is suitable high temperature viscosity, improve the processability of glass, optimizes the striped degree of glass；Further, work as ZnO/Gd₂O₃Value 0.3 hereinafter, can also reduce the thermal expansion coefficient of glass.Therefore ZnO/Gd in the present invention₂O₃Value be 0.5 hereinafter, preferably 0.3 hereinafter, more preferably 0.2 or less.

Ta₂O₅Have the function of improving glass refraction and devitrification resistance, by making expensive Ta₂O₅Constituent content exists 10% hereinafter, the material cost of glass can be reduced, therefore can more inexpensively make optical glass.Preferably, by introduce 1% with On Ta₂O₅, the melting temperature of glass can be reduced, energy required for the melting of raw material reduces, therefore can also reduce optical glass Manufacturing cost.Therefore Ta in the present invention₂O₅Content be limited to 0~10%, preferably 0~8%, more preferably 1~6%.

In certain embodiments of the present invention, if Nb₂O₅/(Nb₂O₅+TiO₂+Ta₂O₅) value less than 0.3, the change of glass Learn bad stability, therefore Nb₂O₅/(Nb₂O₅+TiO₂+Ta₂O₅) range be 0.3~1.0；Further, pass through control Nb₂O₅/(Nb₂O₅+TiO₂+Ta₂O₅) range in 0.4~0.9 range, can also make optical glass be easier to obtain low thermal expansion Coefficient optimizes the devitrification resistance energy of glass.Therefore Nb₂O₅/(Nb₂O₅+TiO₂+Ta₂O₅) range preferably from 0.4~0.9, it is more excellent It is selected as 0.5~0.8.

In certain embodiments of the present invention, by making Ta₂O₅/WO₃0.8 hereinafter, can make optical glass that there is conjunction In the case where suitable melting behaviour, lower thermal expansion coefficient and higher hardness, preferably Ta are obtained₂O₅/WO₃For 0.02~ 0.5, more preferable Ta₂O₅/WO₃It is 0.05~0.3.

Rn₂O(Rn₂O is Li₂O、Na₂O、K₂One of O or a variety of) meltbility of glass can be improved, reduce vitrifying Transition temperature, when its content is more than 5%, stability, glass is deteriorated, and refractive index is greatly reduced, it is difficult to obtain desired refraction Rate.Therefore Rn of the present invention₂O content is 0~5%, preferably 0~2%, more preferably 0~1%.In some embodiments, draw Enter Li₂The internal soundness that O will lead to glass in forming process sharply deteriorates, therefore does not introduce Li further preferably₂O。

RO (one of RO MgO, CaO, SrO, BaO or a variety of) can improve the meltbility and devitrification resistance of glass, By controlling its content 10% hereinafter, readily available desired refractive index, and the excess that can inhibit these ingredients contains The devitrification of caused glass.Therefore, RO content of the present invention is 0~10%, preferably 0~5%, more preferably 0~2%.One In a little embodiments, introducing BaO will lead to the bad stability of glass, therefore not introduce BaO further preferably.

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 5%, show The tendency that glass melting is deteriorated, devitrification resistance reduces, therefore Al of the present invention₂O₃Content be 0~5%, preferably 0~2%, More preferably 0~1%, it does not introduce further preferably.

By the Sb for introducing 0~1%₂O₃、SnO₂, SnO and CeO₂One of or various ingredients as clarifying agent, can be with The clarifying effect for improving glass is preferably introduced into 0~0.5% clarifying agent, more preferably introduces 0~0.1% clarifying agent, further It is preferred that not introducing clarifying agent.

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 Weaken visible light transmittance of the invention, therefore it is desirable, especially for the optics glass that the transmitance of visible light region wavelength requires Glass 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.

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 1.88~1.95, preferably 1.89~1.94, more preferably 1.90 ~1.93；Abbe number (ν_d) it is 31~38, preferably 32~37, more preferably 33~36.

<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 3 classes or more, it is more than preferably 2 classes, more preferably 1 Class.

The acidproof effect stability (D of optical glass_A) (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_A) it is 3 classes or more, it is more than preferably 2 classes, more preferably 1 Class.

Thermal expansion coefficient (α_{20~120 DEG C}) according to 20~120 DEG C of the test of method as defined in GB/T7962.16-2010 of values.

Thermal expansion coefficient (the α of optical glass of the invention_{20~120 DEG C}) it is 80 × 10^-7/ K is hereinafter, preferably 78 × 10^-7/K Hereinafter, more preferably 75 × 10^-7/ K or less.

Knoop hardness (H_K) by the test of test method as defined in GB/T7962.18-2010.

Knoop hardness (the H of optical glass of the present invention_K) it is 650 × 10⁷Pa or more, preferably 655 × 10⁷Pa or more, it is more excellent It is selected as 660 × 10⁷Pa or more, further preferably 665 × 10⁷Pa or more.

Devitrification resistance energy test method are as follows: mother glass is cut into 20 × 20 × 10mm specification, being put into temperature is T_g+ 30 minutes are kept the temperature in the Muffle furnace of 230 DEG C of temperature, Xu Leng in heat-preservation cotton is put into after taking-up, observes Surface Crystallization situation after cooling. If glass after cooling has obvious crystallization, the devitrification resistance of glass can be poor, is denoted as " B "；If glass is without obvious crystallization after cooling, Then the devitrification resistance of glass is able to satisfy secondary press requirement, is denoted as " A ".

The devitrification resistance of optical glass of the present invention can reach A grades, meet the needs of secondary press production blank.

[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

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

The present embodiment obtains having the optical glass formed shown in 1~table of table 3 using the manufacturing method of above-mentioned optical 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 3, It is middle to indicate ZnO/Gd with K1₂O₃；K2 indicates 3 × SiO₂/WO₃；K3 indicates Gd₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃)；K4 indicates Ta₂O₅/ WO₃；K5 indicates B₂O₃/WO₃；K6 indicates (Gd₂O₃+WO₃)/(La₂O₃+TiO₂+ZrO₂)；K7 indicates Nb₂O₅/(Nb₂O₅+TiO₂+ Ta₂O₅)；K8 indicates (Gd₂O₃+La₂O₃)/(WO₃+Nb₂O₅)。

Table 1

Table 2

Table 3

The means of the obtained glass of optical glass Examples 1 to 30 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..

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.

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

1. optical glass, which is characterized in that its component indicates by weight percentage, contains: La₂O₃: 15~40%；Gd₂O₃: 10~ 30%；WO₃: 10~30%；TiO₂: 0~10%；ZrO₂: 0~10%, wherein (Gd₂O₃+WO₃)/(La₂O₃+TiO₂+ZrO₂) be 0.6~2.5.

2. optical glass according to claim 1, which is characterized in that its component indicates by weight percentage, also contains: B₂O₃: 5~20%；SiO₂: 0~10%；Y₂O₃: 0~10%；Yb₂O₃: 0~8%；Ta₂O₅: 0~10%；Nb₂O₅: 0~10%； ZnO:0~10%；Al₂O₃: 0~5%；RO:0~10%；Rn₂O:0~5%, wherein RO is one in MgO, CaO, SrO, BaO Kind or a variety of, Rn₂O is Li₂O、Na₂O、K₂One of O or a variety of.

3. optical glass, which is characterized in that its component indicates by weight percentage, contains: B₂O₃: 5~20%；SiO₂: 0~ 10%；La₂O₃: 15~40%；Gd₂O₃: 10~30%；WO₃: 10~30%；ZrO₂: 0~10%；Nb₂O₅: 0~10%.

4. optical glass according to claim 3, which is characterized in that its component indicates by weight percentage, also contains: Y₂O₃: 0~10%；And/or Yb₂O₃: 0~8%；And/or Ta₂O₅: 0~10%；And/or ZnO:0~10%；And/or TiO₂: 0 ~10%；And/or Al₂O₃: 0~5%；And/or RO:0~10%；And/or Rn₂O:0~5%, wherein RO be MgO, CaO, SrO, One of BaO or a variety of, Rn₂O is Li₂O、Na₂O、K₂One of O or a variety of.

5. optical glass described in any claim according to claim 1~4, which is characterized in that its component percentage by weight Than indicating, (Gd₂O₃+WO₃)/(La₂O₃+TiO₂+ZrO₂) it is 0.6~2.5, preferably (Gd₂O₃+WO₃)/(La₂O₃+TiO₂+ZrO₂) be 0.7~2.0, more preferable (Gd₂O₃+WO₃)/(La₂O₃+TiO₂+ZrO₂) it is 0.8~1.8, further preferred (Gd₂O₃+WO₃)/ (La₂O₃+TiO₂+ZrO₂) it is 1.0~1.5.

6. optical glass described in any claim according to claim 1~4, which is characterized in that its component percentage by weight Than indicating, Gd₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) it is 0.15~0.7, preferably Gd₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) it is 0.2~0.6, More preferable Gd₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) it is 0.3~0.55.

7. optical glass described in any claim according to claim 1~4, which is characterized in that its component percentage by weight Than indicating, 3 × SiO₂/WO₃It is 0.05~1.5, preferably 3 × SiO₂/WO₃It is 0.1~1.0, more preferable 3 × SiO₂/WO₃It is 0.2 ~0.8.

8. optical glass described in any claim according to claim 1~4, which is characterized in that its component percentage by weight Than indicating, B₂O₃/WO₃It is 0.2~1.5, preferably B₂O₃/WO₃It is 0.3~1.0, more preferable B₂O₃/WO₃It is 0.4~0.8.

9. optical glass described in any claim according to claim 1~4, which is characterized in that its component percentage by weight Than indicating, (Gd₂O₃+La₂O₃)/(WO₃+Nb₂O₅) it is 0.8~3.5, preferably (Gd₂O₃+La₂O₃)/(WO₃+Nb₂O₅) be 1.0~ 3.0, more preferable (Gd₂O₃+La₂O₃)/(WO₃+Nb₂O₅) it is 1.5~2.5.

10. optical glass described in any claim according to claim 1~4, which is characterized in that its component percentage by weight Than indicating, ZnO/Gd₂O₃Value be 0.5 hereinafter, it is preferred that ZnO/Gd₂O₃Value be 0.3 hereinafter, more preferable ZnO/Gd₂O₃Value be 0.2 or less.

11. optical glass described in any claim according to claim 1~4, which is characterized in that its component percentage by weight Than indicating, Nb₂O₅/(Nb₂O₅+TiO₂+Ta₂O₅) it is 0.3~1.0, preferably Nb₂O₅/

(Nb₂O₅+TiO₂+Ta₂O₅) it is 0.4~0.9, more preferable Nb₂O₅/(Nb₂O₅+TiO₂+Ta₂O₅) it is 0.5~0.8.

12. optical glass described in any claim according to claim 1~4, which is characterized in that its component percentage by weight Than indicating, Ta₂O₅/WO₃For 0.8 hereinafter, it is preferred that Ta₂O₅/WO₃It is 0.02~0.5, more preferable Ta₂O₅/WO₃It is 0.05~0.3.

13. optical glass described in any claim according to claim 1~4, which is characterized in that its component percentage by weight Than indicating, contain: B₂O₃: 8~18%；And/or SiO₂: 1~8%；And/or La₂O₃: 21~36%；And/or Gd₂O₃: 13~ 26%；And/or WO₃: 12~26%；And/or ZrO₂: 1~8%；And/or Nb₂O₅: 1~8%；And/or Y₂O₃: 0~5%；With/ Or Yb₂O₃: 0~5%；And/or Ta₂O₅: 0~8%；And/or ZnO:0~8%；And/or Al₂O₃: 0~2%；And/or TiO₂: 0 ~5%；And/or RO:0~5%；And/or Rn₂O:0~2%, wherein RO is one of MgO, CaO, SrO, BaO or a variety of, Rn₂O is Li₂O、Na₂O、K₂One of O or a variety of.

14. optical glass described in any claim according to claim 1~4, which is characterized in that its component percentage by weight Than indicating, contain: B₂O₃: 10~15%；And/or SiO₂: 1~6%；And/or La₂O₃: 26~35%；And/or Gd₂O₃: 16~ 25%；And/or WO₃: 15~25%；And/or ZrO₂: 2~7%；And/or Nb₂O₅: 2~6%；And/or Y₂O₃: 0~2%；With/ Or Yb₂O₃: 0~1%；And/or Ta₂O₅: 1~6%；And/or ZnO:0~3%；And/or TiO₂: 0~3%；And/or Al₂O₃: 0 ~1%；And/or RO:0~2%；And/or Rn₂O:0~1%, wherein RO is one of MgO, CaO, SrO, BaO or a variety of, Rn₂O is Li₂O、Na₂O、K₂One of O or a variety of.

15. optical glass described in any claim according to claim 1~4, which is characterized in that its component percentage by weight Than indicating that the clarifying agent containing 0~1%, the clarifying agent are Sb₂O₃、SnO₂, SnO and CeO₂One of or it is a variety of.

16. 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 1.88~1.95, preferably 1.89~1.94, more preferably 1.90~1.93；Abbe number vd is 31~38, preferably It is 32~37, more preferably 33~36.

17. 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 acidproof effect stability D_AMore than 2 classes, preferably 1 class；With/ Or thermalexpansioncoefficientα_{20~120 DEG C}It is 80 × 10^-7/ K is hereinafter, preferably 78 × 10^-7/ K is hereinafter, more preferably 75 × 10^-7/ K or less； And/or Knoop hardness H_KIt is 650 × 10⁷Pa or more, preferably 655 × 10⁷Pa or more, more preferably 660 × 10⁷Pa or more, into One step is preferably 665 × 10⁷Pa or more.

18. gas preform is made of optical glass described in claim 1~17 any claim.

19. optical element is made of optical glass described in claim 1~17 any claim, or is wanted using right Gas preform described in asking 18 is made.

20. optical instrument containing optical glass described in claim 1~17 any claim, or contains claim 19 The optical element.