CN109970337A

CN109970337A - Optical glass, gas preform, optical element and optical instrument

Info

Publication number: CN109970337A
Application number: CN201910348634.9A
Authority: CN
Inventors: 孙伟
Original assignee: Chengdu Guangming Optoelectronics Co Ltd
Current assignee: CDGM Glass Co Ltd; Chengdu Guangming Optoelectronics Co Ltd
Priority date: 2019-04-28
Filing date: 2019-04-28
Publication date: 2019-07-05
Anticipated expiration: 2039-04-28
Also published as: CN109970337B

Abstract

It is 1.71~1.80 that the present invention, which provides a kind of refractive index, and the optical glass that Abbe number is 48~56, component in terms of weight percentage, contains: B₂O₃: 20~40%, La₂O₃: 20~45%, Gd₂O₃: 6~35%, Y₂O₃: 0~15%, wherein Gd₂O₃/(Gd₂O₃+Y₂O₃) it is 0.5~1.0.It is designed by reasonable component, while making the optical glass obtained that there is desired refractive index and Abbe number, there is excellent chemical stability.

Description

Optical glass, gas preform, optical element and optical instrument

Technical field

It is 1.71~1.80 more particularly, to a kind of refractive index the present invention relates to a kind of optical glass, Abbe number is 48~ 56 optical glass, and the gas preform made of the optical glass, optical element and optical instrument.

Background technique

With the development of photovoltaic industry, miniaturization, lightweight, the requirement of high performance are proposed to optical element, this is just So that refractive index is 1.71~1.80, the demand for the optical glass that Abbe number is 48~56 is increasing.In current document, Such glass mostly uses borate glass system to make basis, then adds a certain amount of rare earth oxide, alkaline earth oxide And alkali metal oxide.B in glass system₂O₃When content is larger, chemical stability tends to be deteriorated.Optical element is adding In work and assembly use process, since the chemical stability of optical glass is bad, cause the resistance to corrosion of optical element poor, Irregular dotted or sheet spot is generated on optical element, these spots have very strong destructiveness, will cause optics instrument The performance and feature dissatisfaction of device, until optical property distortion and scrap, seriously affected the service life of optical instrument.Cause The chemical stability of this optical glass is most important for the service precision of instrument and service life.Therefore in B₂O₃The biggish feelings of content Under condition, the chemical stability of glass how is promoted, is a urgent problem to be solved.

Summary of the invention

Based on the above reasons, technical problem to be solved by the invention is to provide a kind of light with superior chemical stability Learn glass.

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

(1) optical glass, component in terms of weight percentage, contain: B₂O₃: 20~40%, La₂O₃: 20~45%, Gd₂O₃: 6~35%, Y₂O₃: 0~15%, wherein Gd₂O₃/(Gd₂O₃+Y₂O₃) it is 0.5~1.0.

(2) optical glass as described in (1), component in terms of weight percentage, also contain: SiO₂: 0~10%, ZrO₂: 0~10%, ZnO:0~9.5%, Yb₂O₃: 0~10%, WO₃: 0~5%, TiO₂: 0~5%, RO:0~10%, Rn₂O: 0~10%, Al₂O₃: 0~5%, Ta₂O₅: 0~5%, Nb₂O₅: 0~10%, clarifying agent: 0~2%, the RO be MgO, CaO, One of SrO, BaO or a variety of, Rn₂O is Li₂O、Na₂O、K₂One of O or a variety of, clarifying agent Sb₂O₃、SnO₂、SnO And CeO₂One of or it is a variety of.

(3) optical glass contains B₂O₃And La₂O₃, component in terms of weight percentage, contains 6~35% Gd₂O₃With 0~15% Y₂O₃, and Gd₂O₃/(Gd₂O₃+Y₂O₃) it is 0.5~1.0, the refractive index nd of the optical glass is 1.71~1.80, Abbe number vd is 48~56, water-fast effect stability D_WMore than 2 classes.

(4) optical glass as described in (3), component in terms of weight percentage, contain B₂O₃: 20~40%, La₂O₃: 20~45%, SiO₂: 0~10%, ZrO₂: 0~10%, ZnO:0~9.5%, Yb₂O₃: 0~10%, WO₃: 0~5%, TiO₂: 0 ~5%, RO:0~10%, Rn₂O:0~10%, Al₂O₃: 0~5%, Ta₂O₅: 0~5%, Nb₂O₅: 0~10%, clarifying agent: 0 ~2%, the RO are one of MgO, CaO, SrO, BaO or a variety of, Rn₂O is Li₂O、Na₂O、K₂One of O or a variety of, Clarifying agent is Sb₂O₃、SnO₂, SnO and CeO₂One of or it is a variety of.

(5) optical glass as described in (1)~(4) are any, component in terms of weight percentage, meet following 6 kinds of feelings One of shape or more than one:

1)ZnO/Y₂O₃It is 1.0 or less；

2)(Y₂O₃+ZrO₂)/La₂O₃It is 0.02~0.6；

3)(SiO₂+ZnO)/La₂O₃It is 0.01~0.45；

4)(Rn₂O+Ta₂O₅)/(SiO₂+ZrO₂) it is 0.5 or less；

5)(Rn₂O+RO)/Y₂O₃It is 0.5 or less；

6)B₂O₃/(SiO₂+La₂O₃+Y₂O₃) it is 0.35~1.0.

(6) optical glass as described in (1)~(4) are any, component is in terms of weight percentage, in which: B₂O₃: 23~ 36%, and/or La₂O₃: 25~40%, and/or Y₂O₃: 1~10%, and/or Nb₂O₅: 0~5%, and/or ZrO₂: 0.5~ 8%, and/or ZnO:0~6%, and/or SiO₂: 0~8%, and/or Gd₂O₃: 12~30%, and/or Yb₂O₃: 0~5% and/ Or WO₃: 0~3%, and/or TiO₂: 0~3%, and/or RO:0~5%, and/or Rn₂O:0~5%, and/or Al₂O₃: 0~ 3%, and/or Ta₂O₅: 0~3%, and/or clarifying agent: 0~1%, the RO are one of MgO, CaO, SrO, BaO or more Kind, Rn₂O is Li₂O、Na₂O、K₂One of O or a variety of, clarifying agent Sb₂O₃、SnO₂, SnO and CeO₂One of or it is a variety of.

(7) optical glass as described in (1)~(4) are any, component in terms of weight percentage, meet following 7 kinds of feelings One of shape or more than one:

1)Gd₂O₃/(Gd₂O₃+Y₂O₃) it is 0.6~0.95；

2)ZnO/Y₂O₃It is 0.8 or less；

3)(Y₂O₃+ZrO₂)/La₂O₃It is 0.05~0.5；

4)(SiO₂+ZnO)/La₂O₃It is 0.03~0.35；

5)(Rn₂O+Ta₂O₅)/(SiO₂+ZrO₂) it is 0.3 or less；

6)(Rn₂O+RO)/Y₂O₃It is 0.3 or less；

7)B₂O₃/(SiO₂+La₂O₃+Y₂O₃) it is 0.45~0.9.

(8) optical glass as described in (1)~(4) are any, component is in terms of weight percentage, in which: B₂O₃: 25~ 35%, and/or La₂O₃: 30~40%, and/or Y₂O₃: 2~8%, and/or Nb₂O₅: 0~2%, and/or ZrO₂: 1~5%, And/or ZnO:0~4%, and/or SiO₂: 1~6%, and/or Gd₂O₃: 15~25%, and/or Yb₂O₃: 0~3%, and/or WO₃: 0~2%, and/or TiO₂: 0~2%, and/or RO: less than 1%, and/or Rn₂O: less than 1%, and/or Al₂O₃: 0~ 2%, and/or Ta₂O₅: 0~2%, and/or clarifying agent: 0~0.5%, the RO are one of MgO, CaO, SrO, BaO or more Kind, Rn₂O is Li₂O、Na₂O、K₂One of O or a variety of, clarifying agent Sb₂O₃、SnO₂, SnO and CeO₂One of or it is a variety of.

(9) optical glass as described in (1)~(4) are any, component in terms of weight percentage, meet following 7 kinds of feelings One of shape or more than one:

1)Gd₂O₃/(Gd₂O₃+Y₂O₃) it is 0.7~0.9；

2)ZnO/Y₂O₃It is 0.5 or less；

3)(Y₂O₃+ZrO₂)/La₂O₃It is 0.1~0.4；

4)(SiO₂+ZnO)/La₂O₃It is 0.05~0.25；

5)(Rn₂O+Ta₂O₅)/(SiO₂+ZrO₂) it is 0.2 or less；

6)(Rn₂O+RO)/Y₂O₃It is 0.2 or less；

7)B₂O₃/(SiO₂+La₂O₃+Y₂O₃) it is 0.5~0.8.

(10) optical glass as described in (1)~(4) are any, component in terms of weight percentage, ZnO/Y₂O₃It is 0.4 Below, and/or (Y₂O₃+ZrO₂)/La₂O₃For 0.15~0.35, and/or (Rn₂O+Ta₂O₅)/(SiO₂+ZrO₂) be 0.1 or less, And/or (Rn₂O+RO)/Y₂O₃It is 0.1 or less.

(11) optical glass as described in (1)~(4) are any without F, and/or is free of WO in component₃, and/or it is free of TiO₂, and/or without RO, and/or be free of Rn₂O, and/or be free of Ta₂O₅, and/or be free of Al₂O₃, the RO be MgO, CaO, One of SrO, BaO or a variety of, Rn₂O is Li₂O、Na₂O、K₂One of O or a variety of.

(12) the refractive index nd of the optical glass as described in (1)~(4) are any be 1.71~1.80, preferably 1.72~ 1.78, more preferably 1.73~1.77, further preferably 1.74~1.77；Abbe number vd is 48~56, preferably 49~55, More preferably 50~54, further preferably 51~53.

(13) the water-fast effect stability D of the optical glass as described in (1)~(4) are any_WMore than 2 classes, preferably 1 Class；And/or Knoop hardness H_KIt is 700 × 10⁷Pa or more, preferably 710 × 10⁷Pa or more, more preferably 720 × 10⁷Pa with On, further preferably 725 × 10⁷Pa or more；And/or density p is 4.60g/cm³Hereinafter, preferably 4.50g/cm³Hereinafter, more Preferably 4.45g/cm³Below；Thermalexpansioncoefficientα_-30/70℃It is 80 × 10^-7/ K is hereinafter, preferably 70 × 10^-7/ K is hereinafter, more excellent It is selected as 65 × 10^-7/ K or less；And/or λ₈₀Less than or equal to 400nm, preferably λ₈₀Less than or equal to 390nm, more preferable λ₈₀It is less than Or it is equal to 385nm；And/or λ₅Less than or equal to 310nm, preferably λ₅Less than or equal to 300nm, more preferable λ₅It is less than or equal to 295nm。

The present invention also provides a kind of gas preforms:

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

The present invention also provides a kind of optical elements:

(15) optical element, using gas preform system described in (1)~(13) any optical glass or (14) At.

The present invention also provides a kind of optical instruments:

(16) optical instrument is made of optical element described in (1)~(13) any optical glass or (15).

The beneficial effects of the present invention are: designing by reasonable component, make the optical glass obtained that there is desired refraction Chemical stability is excellent while rate and Abbe number.

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 the purport invented therefore is limited, in the following contents, optics of the present invention Glass is sometimes 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, total content are all using the weight hundred of the glass substance total amount relative to the composition for being converted into oxide Divide than indicating.Herein, described " composition for being converted into oxide " refers to, the original as optical glass constituent of the invention In the case that oxide, complex salt and the hydroxide etc. expected and used decompose when melting and are changed into oxide, by the oxidation The substance total amount of object 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.

B₂O₃It is a kind of component for forming glass network structure, is the necessary component in the present invention, especially containing a large amount of La₂O₃And Gd₂O₃In the case where contour refractive index component, need to increase B₂O₃To maintain to form the stability of glass.In order to reach Said effect, present invention introduces 20% or more or more B₂O₃, it is preferably introduced into 23% or more B₂O₃, more preferably introduce 25% Above B₂O₃；But when its introduction volume is more than 40%, then the chemical stability decline of glass, and refractive index declines, therefore, B of the invention₂O₃Upper content limit be 40%, preferred upper limit 36%, the more preferable upper limit be 35%.

SiO₂Equally it is that glass network generates body, is the skeleton of optical glass, has and promote chemical durability of glass, maintain The effect of glass devitrification resistance energy；But work as SiO₂When content is higher than 10%, then glass becomes infusibility, and can not obtain institute of the present invention The refractive index needed.Therefore, SiO₂Content be 0~10%, preferred scope be 0~8%, more preferable 1~6%.

La₂O₃It is the necessary component of optical characteristics needed for obtaining the present invention, in inventive formulation system, B₂O₃With La₂O₃ Combination exist, the devitrification resistance property of glass can be effectively improved, and improve the chemical stability of glass.Work as La₂O₃Content When less than 20%, it is difficult to optical characteristics required for realizing；But when its content is more than 45%, glass devitrification resistance and meltbility It can deteriorate instead.Therefore, La of the invention₂O₃Content be 20~45%, preferably 25~40%, more preferably 30~40%.

Gd₂O₃It is effectively, when it contains for the chemical stability and refractive index that improve glass in optical glass of the present invention When amount is lower than 6%, sufficient effect cannot be obtained；But when its content is more than 35%, the devitrification resistance of glass is deteriorated, glass Transition temperature increases.Therefore Gd in the present invention₂O₃Content be 6~35%, preferably 12~30%, more preferably 15~25%.

The component of the high refractive low dispersive effect of the present invention preferably also introduces 15% Y below₂O₃, by introducing Y simultaneously₂O₃ With La₂O₃It matches, while maintaining high refractive index and low dispersion, improves meltbility, the devitrification resistance of glass, if its content More than 15%, stability, the devitrification resistance of glass are reduced.In some embodiments, pass through the Y of 1% or more introducing₂O₃, may be used also Reduce devitrification of glass ceiling temperature and specific gravity.Therefore, Y in the present invention₂O₃Content be 0~15%, preferably 1~10%, it is more excellent It is selected as 2~8%.

Inventor's lot of experiments discovery, in optical glass of the present invention, by making Gd₂O₃With Gd₂O₃And Y₂O₃Conjunction Count content (Gd₂O₃+Y₂O₃) ratio Gd₂O₃/(Gd₂O₃+Y₂O₃) in 0.5~1.0 range, optical glass can be made to have excellent Chemical stability and striped degree；In some embodiments, especially make Gd₂O₃/(Gd₂O₃+Y₂O₃) in 0.6~0.95 range It is interior, it also can get the optical glass with low thermal coefficient of expansion.Therefore, Gd₂O₃/(Gd₂O₃+Y₂O₃) it is 0.5~1.0, preferably Gd₂O₃/(Gd₂O₃+Y₂O₃) it is 0.6~0.95, more preferable Gd₂O₃/(Gd₂O₃+Y₂O₃) it is 0.7~0.9.

In the present invention, by controlling B₂O₃With SiO₂、La₂O₃、Y₂O₃Total content (SiO₂+La₂O₃+Y₂O₃) ratio B₂O₃/(SiO₂+La₂O₃+Y₂O₃) in 0.35~1.0 range, the stability to form glass can be improved, especially control B₂O₃/ (SiO₂+La₂O₃+Y₂O₃) in 0.45~0.9 range, while can also making glass that there is low-density, optimize the striped degree of glass. Therefore, B₂O₃/(SiO₂+La₂O₃+Y₂O₃) it is 0.35~1.0, preferably 0.45~0.9, more preferably 0.5~0.8.

Yb₂O₃It is also a kind of component for assigning high refraction, low dispersion, is a kind of optional components in the present invention, when it When introduction volume is more than 10%, the devitrification resistance of glass can decline with chemical stability, therefore its content is limited to 0~10%, Preferably 0~5%, more preferably 0~3%.

ZrO₂It can play the role of improving Glass optical constant and improve chemical stability, but its content is more than 10%, The devitrification resistance of glass can be deteriorated.Therefore, ZrO of the present invention₂Content be 0~10%, preferably 0.5~8%, more preferably 1 ~5%.

In some embodiments of optical glass of the present invention, preferably make (Y₂O₃+ZrO₂)/La₂O₃In 0.02~0.6 range It is interior, it can make optical glass with relatively low thermel expansion coefficient, optimize the hardness and bubble degree of glass, more preferable (Y₂O₃ +ZrO₂)/La₂O₃It is 0.05~0.5, further preferred (Y₂O₃+ZrO₂)/La₂O₃It is 0.1~0.4, still more preferably (Y₂O₃+ ZrO₂)/La₂O₃It is 0.15~0.35.

ZnO is added in this system glass, and the refractive index and dispersion of adjustable glass reduce the transition temperature of glass, but When its content is more than 9.5%, the devitrification resistance of glass can decline, while high temperature viscosity is smaller, bring difficulty to molding, and increase Add the thermal expansion coefficient and thermal refractive index coefficient of glass.Therefore, the present invention in ZnO content be 0~9.5%, preferably 0~ 6%, more preferably 0~4%.

In certain embodiments of the present invention, by making ZnO/Y₂O₃1.0 hereinafter, optical glass can be made with excellent Chemical stability and lower thermal expansion coefficient, especially make ZnO/Y₂O₃0.8 hereinafter, can also optimize the viscosity of glass, change The processability of kind glass.Therefore ZnO/Y₂O₃Range 1.0 hereinafter, preferably 0.8 hereinafter, more preferably 0.5 hereinafter, into One step is preferably 0.4 or less.

In certain embodiments of the present invention, as (SiO₂+ZnO)/La₂O₃When lower than 0.01, the light transmission rate of glass becomes Difference, as (SiO₂+ZnO)/La₂O₃When higher than 0.45, design requirement is not achieved in the refractive index of glass, and hardness is deteriorated.Therefore, this hair In bright some embodiments, (SiO₂+ZnO)/La₂O₃Range be 0.01~0.45, preferably 0.03~0.35, more preferably It is 0.05~0.25.

WO₃It is high-refraction high-dispersion component, adjustable optical constant in glass of the present invention is added, improves devitrification resistance energy Power.But if the constituent content is excessive, then, it is seen that the transmitance in shortwave area, light area reduces.Therefore, WO in the present invention₃Contain Amount is for 5% hereinafter, preferably 3% hereinafter, more preferably 2% hereinafter, do not introduce further preferably.

TiO₂It is a kind of high-refraction high-dispersion oxide, the refractive index and color of glass can be obviously improved by being added in glass It dissipates, if but excessive TiO₂It is added in glass, it is difficult to realize the development target of low dispersion, while the transmitance of glass can significantly drop Low, the stability of glass can also be deteriorated.Therefore, TiO₂Content be 5% hereinafter, preferably 3% hereinafter, more preferably 2% with Under, it does not introduce further preferably.

Nb₂O₅The refractive index that glass can be improved improves the chemical stability and devitrification resistance of glass, if but its content mistake Greatly, the dispersion of glass can rise, it is difficult to and the glass of objective optics constant is obtained, while will increase the cost and density of glass, and Shortwave transmitance decline in visible region, therefore 10% Nb below is introduced in the present invention₂O₅, the amount of being preferably introduced into be 5% with Under, more preferable introduction volume is 2% hereinafter, not introducing further preferably.

Rn₂O is alkali metal oxide, Rn₂O is Li₂O、Na₂O or K₂One of O or a variety of can improve the molten of glass Melting property reduces glass transition temperature, works as Rn₂When the content of O is more than 10%, stability, glass is deteriorated, therefore Rn of the present invention₂O contains Amount is 0~10%, preferably 0~5%, more preferably less than 1%, is not introduced further preferably.In some implementations of the invention In mode, even if a small amount of contains Li₂O, the chemical stability for also resulting in glass are deteriorated, and crystallization property degenerates, therefore one In a little embodiments, Li is not contained particularly preferably₂O。

Ta₂O₅Have the function of improving refractive index, but its too high levels, the stability decline of glass, and optical constant is difficult to Control desired range；On the other hand, compared with other compositions, Ta₂O₅Price it is very expensive, from practical and cost Angle considers, should reduce its usage amount to the greatest extent.Therefore, Ta of the invention₂O₅Content is limited to 0~5%, preferably 0~3%, more Preferably 0~2%.In some embodiments, even if a small amount of contains Ta₂O₅, the bad stability of glass is also resulted in, because This does not contain Ta particularly preferably in some embodiments₂O₅。

In certain embodiments of the present invention, Rn₂O and Ta₂O₅Total content (Rn₂O+Ta₂O₅) and SiO₂And ZrO₂'s Total content (SiO₂+ZrO₂) between ratio (Rn₂O+Ta₂O₅)/(SiO₂+ZrO₂) more than 0.5, then the hardness of optical glass becomes Difference, while glass metal increases the corrosion of melting tank, the light transmission rate of optical glass reduces.Therefore (Rn₂O+Ta₂O₅)/(SiO₂+ ZrO₂) it is 0.5 hereinafter, it is preferred that (Rn₂O+Ta₂O₅)/(SiO₂+ZrO₂) it is 0.3 hereinafter, more preferably (Rn₂O+Ta₂O₅)/(SiO₂+ ZrO₂) it is 0.2 hereinafter, further preferably (Rn₂O+Ta₂O₅)/(SiO₂+ZrO₂) it is 0.1 or less.

RO is alkaline earth oxide, is one of BaO, SrO, CaO or MgO or a variety of.RO is added can be in glass Improve the meltbility of glass, reduce glass transition temperature, but when the content of RO is more than 10%, the devitrification resistance of glass drops It is low.Therefore, RO content of the present invention is 0~10%, preferably 0~5%, more preferably less than 1%, is not introduced further preferably. In some embodiments, even if a small amount of crystallization property for also resulting in glass containing BaO aggravates, therefore in some realities It applies in mode, does not contain BaO particularly preferably.

In certain embodiments of the present invention, Rn₂The total content and Y of O and RO₂O₃Between ratio (Rn₂O+RO)/ Y₂O₃More than 0.5, the devitrification resistance of optical glass can be reduced with chemical stability, the decline of bubble degree, therefore (Rn₂O+RO)/Y₂O₃ For 0.5 hereinafter, preferably 0.3 hereinafter, more preferably 0.2 hereinafter, further preferably 0.1 or less.

Al₂O₃The chemical stability of glass can be improved, but when its content is more than 5%, the dispersion of glass increases, and meltbility becomes Difference.Therefore, Al of the present invention₂O₃Content be 0~5%, preferably 0~3%, more preferably 0~2%, do not draw further preferably Enter.

By adding Sb on a small quantity₂O₃、SnO、SnO₂、CeO₂One of component is a variety of as clarifying agent, and glass can be improved The clarifying effect of glass, but work as Sb₂O₃When content is more than 2%, glass has the tendency that Clarification Performance reduction, simultaneously because its Strong oxdiative Effect promotes the corrosion of the platinum or platinum alloy vessel of melted glass and the deterioration of molding die, therefore the present invention is preferred Sb₂O₃Additive amount be 0~2%, more preferably 0~1%, further preferred 0~0.5%.SnO and SnO₂It can also be used as clear Clear agent is added, but when its content is more than 2%, then glass can colour, or when heating, soften glass and carry out die forming When Deng shaping again, Sn can become the starting point that nucleus generates, and generate the tendency of devitrification.Therefore SnO of the invention₂Content it is preferred It is 0~2%, more preferably 0~1%, further preferred 0~0.5%, does not contain still more preferably；The content of SnO is preferably 0~2%, more preferably 0~1%, further preferred 0~0.5%, it does not contain still more preferably.CeO₂Effect and addition Amount ratio and SnO₂Unanimously, content is preferably 0~2%, and more preferably 0~1%, further preferred 0~0.5%, more into one Step does not preferably contain.

F can reduce glass dispersion, improve glass devitrification resistance energy, but it can make glass in melting and the volatilization of forming process The data fluctuations of glass become larger, while the volatilization of F will lead to the generation of striped in forming process；In addition, the volatilization of F can be to human body Potential security threat is generated with environment.In the present invention F content be limited at 4% hereinafter, preferably 3% hereinafter, more preferably 1% hereinafter, do not introduce still more preferably.

In order to preferably reach the purpose of the present invention, and the excellent optical glass of properties is obtained, in glass of the present invention Each component indicates by weight percentage, preferably SiO₂、B₂O₃、La₂O₃、Gd₂O₃、Y₂O₃And ZrO₂Total content be 95% or more； More preferable SiO₂、B₂O₃、La₂O₃、Gd₂O₃、Y₂O₃And ZrO₂Total content be 97% or more；Further preferred SiO₂、B₂O₃、 La₂O₃、Gd₂O₃、Y₂O₃、ZrO₂, ZnO and Sb₂O₃Total content be 99% or more.

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.

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

The refractive index (nd) of optical glass of the present invention is 1.71~1.80, preferably 1.72~1.78, more preferably 1.73 ~1.77, further preferably 1.74~1.77；Abbe number (vd) is 48~56, preferably 49~55, more preferably 50~54, Further preferably 51~53.

<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.

The density (ρ) of optical glass is tested by method as defined in GB/T7962.20-2010.

The density (ρ) of optical glass of the present invention is 4.60g/cm³Hereinafter, preferably 4.50g/cm³Hereinafter, more preferably 4.45g/cm³Below.

Knoop hardness (the H of optical glass_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 700 × 10⁷Pa or more, preferably 710 × 10⁷Pa or more, it is more excellent It is selected as 720 × 10⁷Pa or more is still more preferably 725 × 10⁷Pa or more.

Thermal expansion coefficient (the α of optical glass of the present invention_-30/70℃) according to the test of method as defined in GB/T7962.16-2010- 30~70 DEG C of data.

Thermal expansion coefficient (the α of optical glass of the invention_-30/70℃) it is 80 × 10^-7/ K is hereinafter, preferably 70 × 10^-7/K Hereinafter, more preferably 65 × 10^-7/ K or less.

The degree of staining λ of optical glass of the present invention₈₀/λ₅It indicates.λ₈₀Refer to that glass transmittance reaches corresponding wave when 80% It is long, λ₅Refer to that glass transmittance reaches corresponding wavelength when 5%.Wherein, λ₈₀Measurement be using with parallel to each other and optics The glass with a thickness of 10 ± 0.1mm of the opposite plane of two of polishing, measures the light splitting in the wavelength domain from 280nm to 700nm Transmissivity and the wavelength for showing transmissivity 80%.So-called spectral transmission or transmissivity are vertical to the above-mentioned surface of glass Ground incident intensity I_inLight, project intensity I through glass and from plane_outLight in the case where pass through I_out/I_inIt indicates Amount, and also contain the transmissivity of the surface reflection loss on the above-mentioned surface of glass.

Optical glass λ of the invention₈₀Less than or equal to 400nm, preferably λ₈₀Range be less than or equal to 390nm, it is more excellent Select λ₈₀Range be less than or equal to 385nm；λ₅Less than or equal to 310nm, preferably λ₅Range be less than or equal to 300nm, More preferable λ₅Range be less than or equal to 295nm.

[manufacturing method of optical glass]

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 1200~1300 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 the optics glass with composition shown in 1~table of table 3 using the manufacturing method of above-mentioned optical glass Glass.In addition, the test method measures the performance of each glass through the invention, and measurement result is indicated in 1~table of table 3 In, Gd is indicated with K1 in 1~table of table 3₂O₃/(Gd₂O₃+Y₂O₃), K2 indicates ZnO/Y₂O₃, K3 expression (Y₂O₃+ZrO₂)/La₂O₃, K4 Indicate (SiO₂+ZnO)/La₂O₃, K5 expression (Rn₂O+Ta₂O₅)/(SiO₂+ZrO₂), K6 indicates (Rn₂O+RO)/Y₂O₃, K7 expression B₂O₃/(SiO₂+La₂O₃+Y₂O₃)。

Table 1

Table 2

Table 3

The obtained optical glass of Examples 1 to 10 in table 1 is cut into predefined size, then is equably coated on the surface Then release agent is heated, softens, is press-formed, make recessed meniscus shaped lens, male bend moon-shaped lens, biconvex lens, The prefabricated component of the various lens such as biconcave lens, plano-convex lens, plano-concave lens, prism.

By obtained these prefabricated components annealing of above-mentioned gas preform 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.Antireflection can be also coated on the surface of gained optical element Film.

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 in terms of weight percentage, contains: B₂O₃: 20~40%, La₂O₃: 20~ 45%, Gd₂O₃: 6~35%, Y₂O₃: 0~15%, wherein Gd₂O₃/(Gd₂O₃+Y₂O₃) it is 0.5~1.0.

2. optical glass as described in claim 1, which is characterized in that its component in terms of weight percentage, also contains: SiO₂: 0~10%, ZrO₂: 0~10%, ZnO:0~9.5%, Yb₂O₃: 0~10%, WO₃: 0~5%, TiO₂: 0~5%, RO:0~ 10%, Rn₂O:0~10%, Al₂O₃: 0~5%, Ta₂O₅: 0~5%, Nb₂O₅: 0~10%, clarifying agent: 0~2%, the RO For one of MgO, CaO, SrO, BaO or a variety of, Rn₂O is Li₂O、Na₂O、K₂One of O or a variety of, clarifying agent are Sb₂O₃、SnO₂, SnO and CeO₂One of or it is a variety of.

3. optical glass contains B₂O₃And La₂O₃, which is characterized in that its component in terms of weight percentage, contains 6~35% Gd₂O₃With 0~15% Y₂O₃, and Gd₂O₃/(Gd₂O₃+Y₂O₃) it is 0.5~1.0, the refractive index nd of the optical glass is 1.71 ~1.80, Abbe number vd are 48~56, water-fast effect stability D_WMore than 2 classes.

4. optical glass as claimed in claim 3, which is characterized in that its component in terms of weight percentage, contains B₂O₃: 20 ~40%, La₂O₃: 20~45%, SiO₂: 0~10%, ZrO₂: 0~10%, ZnO:0~9.5%, Yb₂O₃: 0~10%, WO₃: 0~5%, TiO₂: 0~5%, RO:0~10%, Rn₂O:0~10%, Al₂O₃: 0~5%, Ta₂O₅: 0~5%, Nb₂O₅: 0~ 10%, clarifying agent: 0~2%, the RO are one of MgO, CaO, SrO, BaO or a variety of, Rn₂O is Li₂O、Na₂O、K₂In O One or more, clarifying agent Sb₂O₃、SnO₂, SnO and CeO₂One of or it is a variety of.

5. the optical glass as described in Claims 1 to 4 any claim, which is characterized in that its component is with weight percent Indicate, meet one of following 6 kinds of situations or more than one:

1)ZnO/Y₂O₃It is 1.0 or less；

2)(Y₂O₃+ZrO₂)/La₂O₃It is 0.02~0.6；

3)(SiO₂+ZnO)/La₂O₃It is 0.01~0.45；

4)(Rn₂O+Ta₂O₅)/(SiO₂+ZrO₂) it is 0.5 or less；

5)(Rn₂O+RO)/Y₂O₃It is 0.5 or less；

6)B₂O₃/(SiO₂+La₂O₃+Y₂O₃) it is 0.35~1.0.

6. the optical glass as described in Claims 1 to 4 any claim, which is characterized in that its component is with weight percent It indicates, in which: B₂O₃: 23~36%, and/or La₂O₃: 25~40%, and/or Y₂O₃: 1~10%, and/or Nb₂O₅: 0~5%, And/or ZrO₂: 0.5~8%, and/or ZnO:0~6%, and/or SiO₂: 0~8%, and/or Gd₂O₃: 12~30%, and/or Yb₂O₃: 0~5%, and/or WO₃: 0~3%, and/or TiO₂: 0~3%, and/or RO:0~5%, and/or Rn₂O:0~5%, And/or Al₂O₃: 0~3%, and/or Ta₂O₅: 0~3%, and/or clarifying agent: 0~1%, the RO are MgO, CaO, SrO, BaO One of or a variety of, Rn₂O is Li₂O、Na₂O、K₂One of O or a variety of, clarifying agent Sb₂O₃、SnO₂, SnO and CeO₂In It is one or more.

7. the optical glass as described in Claims 1 to 4 any claim, which is characterized in that its component is with weight percent Indicate, meet one of following 7 kinds of situations or more than one:

1)Gd₂O₃/(Gd₂O₃+Y₂O₃) it is 0.6~0.95；

2)ZnO/Y₂O₃It is 0.8 or less；

3)(Y₂O₃+ZrO₂)/La₂O₃It is 0.05~0.5；

4)(SiO₂+ZnO)/La₂O₃It is 0.03~0.35；

5)(Rn₂O+Ta₂O₅)/(SiO₂+ZrO₂) it is 0.3 or less；

6)(Rn₂O+RO)/Y₂O₃It is 0.3 or less；

7)B₂O₃/(SiO₂+La₂O₃+Y₂O₃) it is 0.45~0.9.

8. the optical glass as described in Claims 1 to 4 any claim, which is characterized in that its component is with weight percent It indicates, in which: B₂O₃: 25~35%, and/or La₂O₃: 30~40%, and/or Y₂O₃: 2~8%, and/or Nb₂O₅: 0~2%, And/or ZrO₂: 1~5%, and/or ZnO:0~4%, and/or SiO₂: 1~6%, and/or Gd₂O₃: 15~25%, and/or Yb₂O₃: 0~3%, and/or WO₃: 0~2%, and/or TiO₂: 0~2%, and/or RO: less than 1%, and/or Rn₂O: less than 1%, and/or Al₂O₃: 0~2%, and/or Ta₂O₅: 0~2%, and/or clarifying agent: 0~0.5%, the RO be MgO, CaO, One of SrO, BaO or a variety of, Rn₂O is Li₂O、Na₂O、K₂One of O or a variety of, clarifying agent Sb₂O₃、SnO₂、SnO And CeO₂One of or it is a variety of.

9. the optical glass as described in Claims 1 to 4 any claim, which is characterized in that its component is with weight percent Indicate, meet one of following 7 kinds of situations or more than one:

1)Gd₂O₃/(Gd₂O₃+Y₂O₃) it is 0.7~0.9；

2)ZnO/Y₂O₃It is 0.5 or less；

3)(Y₂O₃+ZrO₂)/La₂O₃It is 0.1~0.4；

4)(SiO₂+ZnO)/La₂O₃It is 0.05~0.25；

5)(Rn₂O+Ta₂O₅)/(SiO₂+ZrO₂) it is 0.2 or less；

6)(Rn₂O+RO)/Y₂O₃It is 0.2 or less；

7)B₂O₃/(SiO₂+La₂O₃+Y₂O₃) it is 0.5~0.8.

10. the optical glass as described in Claims 1 to 4 any claim, which is characterized in that its component is with weight percent It indicates, ZnO/Y₂O₃For 0.4 or less, and/or (Y₂O₃+ZrO₂)/La₂O₃For 0.15~0.35, and/or (Rn₂O+Ta₂O₅)/(SiO₂ +ZrO₂) it is 0.1 or less, and/or (Rn₂O+RO)/Y₂O₃It is 0.1 or less.

11. the optical glass as described in Claims 1 to 4 any claim, which is characterized in that in its component without F and/ Or be free of WO₃, and/or be free of TiO₂, and/or without RO, and/or be free of Rn₂O, and/or be free of Ta₂O₅, and/or it is free of Al₂O₃, the RO is one of MgO, CaO, SrO, BaO or a variety of, Rn₂O is Li₂O、Na₂O、K₂One of O or a variety of.

12. the optical glass as described in Claims 1 to 4 any claim, which is characterized in that the refractive index nd of optical glass It is 1.71~1.80, preferably 1.72~1.78, more preferably 1.73~1.77, further preferably 1.74~1.77；Abbe Number vd is 48~56, preferably 49~55, more preferably 50~54, further preferably 51~53.

13. the optical glass as described in Claims 1 to 4 any claim, which is characterized in that the water-fast effect of optical glass Stability D_WMore than 2 classes, preferably 1 class；And/or Knoop hardness H_KIt is 700 × 10⁷Pa or more, preferably 710 × 10⁷Pa with On, more preferably 720 × 10⁷Pa or more, further preferably 725 × 10⁷Pa or more；And/or density p is 4.60g/cm³With Under, preferably 4.50g/cm³Hereinafter, more preferably 4.45g/cm³Below；Thermalexpansioncoefficientα_-30/70℃It is 80 × 10^-7/ K hereinafter, Preferably 70 × 10^-7/ K is hereinafter, more preferably 65 × 10^-7/ K or less；And/or λ₈₀Less than or equal to 400nm, preferably λ₈₀It is less than Or it is equal to 390nm, more preferable λ₈₀Less than or equal to 385nm；And/or λ₅Less than or equal to 310nm, preferably λ₅It is less than or equal to 300nm, more preferable λ₅Less than or equal to 295nm.

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

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

16. optical instrument, using described in optical glass described in claim 1~13 any claim or claim 15 Optical element is made.