CN109264989A

CN109264989A - Optical glass, its prefabricated component, optical element and optical instrument

Info

Publication number: CN109264989A
Application number: CN201811138262.9A
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: 2018-09-28
Filing date: 2018-09-28
Publication date: 2019-01-25
Anticipated expiration: 2038-09-28
Also published as: CN109264989B

Abstract

Optical glass, its prefabricated component, optical element and optical instrument of the present invention provide one kind by weight percentage, contain SiO₂: 0-10%, B₂O₃: 5-25%, ZrO₂: 0-15%, ZnO:10-25%, TiO₂+Nb₂O₅+WO₃: 2-30%, Ln₂O₃: the optical glass of 30-55%, the Ln₂O₃For La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃Total content, wherein B₂O₃/Ln₂O₃For 0.3-0.8, Y₂O₃/Gd₂O₃For 0.3-3.The Abbe number (vd) of refractive index (nd) and 38-41 of the optical glass with 1.84-1.87, while devitrification resistance and devitrification resistance can be excellent, chemical stability is good.

Description

Optical glass, its prefabricated component, optical element and optical instrument

Technical field

The invention belongs to optical glass fields, and in particular to a kind of optical glass and its prefabricated component, the optical element of production And optical instrument.

Background technique

Optical glass can be used for manufacturing lens, prism, reflecting mirror in optical instrument etc., the component being made of optical glass It is the key element in optical instrument.With 1.84-1.87 refractive index (nd), 38-41 Abbe number (vd) optical glass because Transmission performance is good, refractive index is high, is widely used in manufacturing camera, telescope, microscope and other precision optical instruments Lens in.In recent years, the number of optical element is reduced using non-spherical lens and then make optical instrument miniaturization and lighting As a main trend, the market demand is also increasingly strong.

But with it is hot-forming be ground and grind again, conventional methods the manufacture non-spherical lens such as melten glass is remanufactured at This height, and flow chart is complicated.Precise compression molding is that a kind of operation is simpler, the lower optical glass material system of cost The method of standby optical element.But the performance of glass material will be put forward higher requirements with this method production non-spherical lens. It is required that being easy to carry out precise compression molding, devitrification resistance is high, and fusing point is low, and bubble degree is excellent etc..If optical element will be used in family In the photographic equipments such as digital camera, the video camera of outer long-time service, optical glass material is also required to have preferable chemical stability, To resist the erosion of water in outdoor environment, acid etc., guarantee the use quality and service life of lens.In addition, for needing in spy The optical instrument to work at different temperature, requires glass material to have good thermal expansion coefficient, also to reduce glass under temperature change Expansion and the degree shunk.

Patent CN104803600A, CN104098267A, CN105819682A etc. each provide refractive index (nd) and Ah Shellfish number (vd) optical glass identical or close with the present invention, but it is not still able to satisfy other above-mentioned requirements.

Summary of the invention

In view of deficiency above-mentioned of the existing technology, the purpose of the present invention is to provide one kind to have 1.84-1.87 folding Penetrate the optical glass of rate (nd), 38-41 Abbe number (vd).The optical glass is easy to carry out precise compression molding, and devitrification Property and devitrification resistance can it is excellent, chemical stability is good, at low cost.

The present invention also provides the prefabricated component made by above-mentioned optical glass, optical element and optical instruments.

Present invention technical solution used for the above purpose is as follows:

Optical glass is contained in terms of weight %: SiO₂: 0-10%, B₂O₃: 5-25%, ZrO₂: 0-15%, ZnO:10- 25%, TiO₂+Nb₂O₅+WO₃: 2-30%, Ln₂O₃: 30-55%, the Ln₂O₃For La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃It is total Content, wherein B₂O₃/Ln₂O₃For 0.3-0.8, Y₂O₃/Gd₂O₃For 0.3-3.

Further, above-mentioned optical glass is also contained in terms of weight %: the Rn of the RO of 0-10%, 0-10%₂O, 0-1% Clarifying agent, the RO is one of MgO, CaO, SrO or BaO or a variety of, the Rn₂O is Li₂O、Na₂O、K₂One in O Kind is a variety of, and the clarifying agent is Sb₂O₃、SnO₂、CeO₂One of or it is a variety of.

Optical glass, in terms of weight %, by the SiO of 0-10%₂, the B of 5-25%₂O₃, the ZrO of 0-15%₂, 10-25%'s The TiO of ZnO, 2-30%₂+Nb₂O₅+WO₃, the Ln of 30-55%₂O₃, the Rn of the RO of 0-10%, 0-10%₂The clarifying agent of O, 0-1% Composition, the Ln₂O₃For La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃Total content, the RO be MgO, CaO, SrO or BaO in one Kind or a variety of, the Rn₂O is Li₂O、Na₂O、K₂One of O or a variety of, the clarifying agent are Sb₂O₃、SnO₂、CeO₂In one Kind is a variety of, wherein B₂O₃/Ln₂O₃For 0.3-0.8, Y₂O₃/Gd₂O₃For 0.3-3.

Further, optical glass above-mentioned, each component content meet one of following 4 kinds of situations or more than one:

1)SiO₂/(SiO₂+B₂O₃) it is 0-0.25；

2)Y₂O₃/Ln₂O₃For 0.08-0.45；

3)Y₂O₃/B₂O₃For 0.15-2；

4)Y₂O₃/(SiO₂+B₂O₃) it is 0.16-0.8.

Further, optical glass above-mentioned, in which: SiO₂: 1-8% and/or B₂O₃: 10-23% and/or ZrO₂: 1- 10% and/or ZnO:10-20% and/or TiO₂+Nb₂O₅+WO₃: 4-22% and/or Ln₂O₃: 35-52% and/or RO:0- 5% and/or R₂O:0-5% and/or clarifying agent 0-0.5%.

Further, optical glass above-mentioned, each component content meet one of following 6 kinds of situations or more than one:

1)SiO₂/(SiO₂+B₂O₃) it is 0.05-0.23；

2)Y₂O₃/Ln₂O₃For 0.1-0.4；

3)Y₂O₃/B₂O₃For 0.2-1.5；

4)Y₂O₃/(SiO₂+B₂O₃) it is 0.2-0.7；

5)B₂O₃/Ln₂O₃For 0.3-0.6；

6)Y₂O₃/Gd₂O₃For 0.5-2.5.

Further, optical glass above-mentioned, in which: SiO₂: 1-4% and/or B₂O₃: 15-20% and/or ZrO₂: 2- 6% and/or ZnO:13-17% and/or TiO₂+Nb₂O₅+WO₃: 10-18% and/or Ln₂O₃: 40-50%.

1)SiO₂/(SiO₂+B₂O₃) it is 0.08-0.2；

2)Y₂O₃/Ln₂O₃For 0.1-0.3；

3)Y₂O₃/B₂O₃For 0.3-1；

4)Y₂O₃/(SiO₂+B₂O₃) it is 0.3-0.6；

5)B₂O₃/Ln₂O₃For 0.3-0.5；

6)Y₂O₃/Gd₂O₃Greater than 1 but it is less than or equal to 2.

Further, optical glass above-mentioned, in which: Nb₂O₅: 1-15% and/or WO₃: 1-15% and/or TiO₂: 0- 10% and/or La₂O₃: 20-45% and/or Gd₂O₃: 0-15% and/or Y₂O₃: 1-15% and/or Yb₂O₃: 0-5%.

Further, optical glass above-mentioned, in which: Nb₂O₅: 2-10% and/or WO₃: 2-12% and/or TiO₂: 0- 5% and/or La₂O₃: 25-40% and/or Gd₂O₃: 1-10% and/or Y₂O₃: 3-15%.

Further, optical glass above-mentioned, in which: Nb₂O₅: 4-8% and/or WO₃: 6-10% and/or La₂O₃: 30- 35% and/or Gd₂O₃: 3-7% and/or Y₂O₃: 6-10%, and/or be free of TiO₂。

Further, optical glass above-mentioned, refractive index (nd) are 1.84-1.87, preferably 1.85-1.86；Abbe Number (vd) is 38.0-41.0, preferably 38.5-40.0.

Further, optical glass above-mentioned, powder method water-resistant stability (D_W) it is 2 classes or more, preferably 1 class, powder Last method acid-resistant stability (D_A) it is 3 classes or more, preferably 2 classes；Its bubble degree is A grades or A grades or more, preferably A₀Grade or A₀With On.

Further, optical glass above-mentioned, thermal expansion coefficient (α_-30℃-70℃)≤75×10^-7/ K, preferably α_-30℃-70℃ ≤70×10^-7/K；Its transition temperature (Tg) is for 640 DEG C hereinafter, preferably 630 DEG C hereinafter, more preferably 625 DEG C or less；It is described The crystallization ceiling temperature of optical glass is for 1250 DEG C hereinafter, preferably 1200 DEG C hereinafter, more preferably 1180 DEG C or less.

Gas preform is made of optical glass above-mentioned.

Optical element is made of optical glass above-mentioned or gas preform.

Optical instrument is made of optical element above-mentioned.

High refractive low dispersive glass material devitrification resistance with higher of the invention, but be easy carry out accurate die pressing at Type, and the content for the high prices raw material such as control rare earth oxide, cost is relatively low, is suitble to be applied to precise compression molding In technique.Meanwhile the present invention enables the chemical stability of glass and devitrification resistance to be improved by reasonable component proportion, mentions The high yield rate of product.Some preferred technical solutions also advanced optimize component proportion, to reduce the thermal expansion system of glass Number optimizes the bubble degree of glass, strengthens chemical stability.For manufacturing quality is more preferable, the optical element of longer life expectancy and optics instrument Device provides the glass material of high performance-price ratio.

Specific embodiment

Optical glass

The composition of optical glass of the invention is described in detail below, when being not particularly illustrated, each glass ingredient Content, total content refer both to weight content, indicated with weight %, be the sum of weight or weight of several components of a certain component Account for the percentage of optical glass total weight；The ratio between each glass ingredient or the ratio between several components adduction, are by its corresponding weight Content makees ratio after making ratio or weight content adduction.

Optical property needed for optical glass of the invention has the lens material for meeting production precision instrument, refractive index It (nd) is 1.84-1.87, Abbe number (vd) is 38-41, and is easy precise compression molding, and chemical stability and bubble degree are excellent It is different.The optical glass is contained in terms of weight %: SiO₂: 0-10%, B₂O₃: 5-25%, ZrO₂: 0-15%, ZnO:10- 25%, TiO₂+Nb₂O₅+WO₃: 2-30%, Ln₂O₃: 30-55%, the Ln₂O₃For La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃It is total Content, also, wherein B₂O₃/Ln₂O₃For 0.3-0.8, Y₂O₃/Gd₂O₃For 0.3-3.

Wherein, B₂O₃It is that glass network forms component, has and improve glass fusible and devitrification resistance.It is above-mentioned in order to reach Effect, present invention introduces 5% or more or more B₂O₃, it is preferably introduced into 10% or more B₂O₃, more preferably introduce 15% or more B₂O₃；But when its introduction volume is more than 25%, then glass declines at glass stability, and refractive index declines, therefore, of the invention B₂O₃Content be set as the upper limit for 25%, preferred upper limit 23%, the more preferable upper limit is 20%.

SiO₂It is a kind of optional component in the present invention, also constitutes glass former.SiO₂What is formed in glass is Oxygen-octahedron three-dimensional network is very fine and close firm.Such network is added in glass, to loose boron oxygen triangle volume grid It is reinforced, so that it is become fine and close, to promote the high temperature viscosity of glass.In addition, SiO₂The content the high more advantageously reduces glass The thermal expansion coefficient of glass.SiO in optical glass of the invention₂The lower limit of content is 0%, preferably 1%；If but SiO₂Content It is excessive, the transition temperature of glass can be made to increase, and reduce the meltbility of glass, increase technology difficulty, therefore its upper content limit It is 10%, preferred upper limit 8%, the further preferred upper limit is 4%.

SiO₂And B₂O₃It is all that glass network forms component, through the present inventor the study found that under formula of the invention, SiO₂/(SiO₂+B₂O₃) it will affect the devitrification resistance energy and thermal expansion coefficient of glass.SiO₂/(SiO₂+B₂O₃) value it is bigger, glass Thermal expansion coefficient it is lower, be more conducive to reduce glass to the sensibility of temperature, but will lead to the devitrification resistance energy of glass simultaneously Deterioration.It has been investigated that working as SiO in formula of the invention₂/(SiO₂+B₂O₃) value in 0-0.25 range, glass can be made Thermal expansion coefficient be lower than 75 × 10^-7/ K, and devitrification resistance can be excellent, and preferred ratio range is 0.05-0.23, more preferably Range be 0.08-0.2.

ZrO₂It is used as optional compositions in the present invention, is a kind of high refractive low dispersive oxide, being added can be in glass It promotes the refractive index of glass and adjusts dispersion.Meanwhile proper amount of ZrO₂It is added in glass, the devitrification resistance of glass can be promoted Energy and chemical stability.But in optical glass of the invention, if its content is higher than 15%, glass can become difficult to melt, Smelting temperature can rise, and inside glass is easy to cause field trash and its transmitance decline occur.Therefore, content is set as 0- 15%, preferably 1-10%, further preferably 2-6%.

The refractive index and dispersion of the adjustable glass of ZnO improve the devitrification resistance energy of glass, reduce the transformation temperature of glass Degree, promotes the chemical stability of glass.ZnO can also reduce the high temperature viscosity of glass, allow glass at a lower temperature Melting, so as to promote the transmitance of glass.But if ZnO additional amount is excessive, the devitrification resistance of glass can decline instead, High temperature viscosity is smaller simultaneously, brings difficulty to molding.Therefore, in glass system of the present invention, the content lower limit of ZnO is set as 10%, preferred lower limit is 13%；The upper content limit of ZnO is set as 25%, and the preferred upper limit is 20%, and the preferred upper limit is 17%.

TiO₂As optional component, the refractive index of glass can be improved, adds TiO in right amount₂It, can be with into glass of the present invention Increase the anti-crystallization stability of glass, and substitution Nb that can be certain₂O₅And WO₃.But too high levels will lead under glass transmitance Drop.In optical glass of the invention, TiO₂Content be 0-10%, preferred content is 0-5%, and preferred content is 0%.

Nb₂O₅It is the component that can improve chemical durability of glass and refractive index.Work as Nb₂O₅Content less than 1% when, optics Design requirement is not achieved in constant；And when its content is more than 15%, the devitrification resistance of glass reduces, therefore, Nb₂O₅Content limit It is set to 1-15%, preferably 2-10%, more preferably 4-8%.

WO₃Main function in glass is to maintain optical constant, improves devitrification of glass performance, but its too high levels, meeting Make the reduction of glass transmitance, degree of staining increases, and crystallization property degenerates.So WO₃Preferred content be 1-15%, more preferably Content is 2-12%, and further preferred content is 6-10%.

Due to TiO₂、Nb₂O₅、WO₃All have the function of improving refractive index but also improve dispersion, therefore, from light of the invention It learns glass to need that there is high refraction, low dispersion and the requirement of high transmittance to set out, by TiO₂+Nb₂O₅+WO₃The upper limit be set as 30%, the preferred upper limit is 22%, and the preferred upper limit is 18%.But work as TiO₂+Nb₂O₅+WO₃It is too low, and will lead to glass Therefore its lower limit is set as 2%, preferred lower limit is 4%, and more preferably lower limit is 10% by the thermostabilization of glass and compressibility decline.

Rare earth oxide Ln is added₂O₃(La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃) refractive index that helps to improve glass, when it When total content is lower than 30%, expected optical constant can not be obtained, but when its total content is more than 55%, the chemical stabilization of glass Property, devitrification resistance will reduce, and the cost of material that glass will be improved.Therefore La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃Total content Ln₂O₃It is set as 30-55%, preferably 35-52%, further preferably 40-50%.

Rare earth oxide Ln₂O₃It is dispersed in glass network, is mainly used for improving refractive index, but present inventor exists It is found in research, glass grid component B₂O₃With Ln₂O₃Ratio have important influence to the chemical stability of glass.Work as B₂O₃/ Ln₂O₃When lower than 0.3, chemical stability, especially acid-resistant stability cannot be met the requirements, and work as B₂O₃/Ln₂O₃When higher than 0.8, Refractive index will reduce again, therefore its range is set as 0.3-0.8, preferably 0.3-0.6, more preferably 0.3-0.5 by the present invention.

La in rare earth oxide₂O₃It is that can improve the component of glass optical characteristic, but when its content is more than 45%, Glass devitrification resistance deteriorates with melting behaviour.It is therefore preferable that La of the invention₂O₃Content be 20-45%, more preferably 25- 40%, further preferably 30-35%.

Gd₂O₃As optional component, the refractive index of glass and the unobvious dispersion for improving glass, the present invention can be increased In by introduce Gd₂O₃, the stability to form glass can be improved, and significantly increase the chemical stability of glass, is maintaining While refractive index, the excessive rising of dispersion is controlled；But if its content is more than 15%, then glass devitrification resistance reduce and glass The density of glass is in rising trend.Therefore, Gd of the invention₂O₃Content be 0-15%, preferred scope 1-10%, more preferable model It encloses for 3-7%.

Y₂O₃It is to maintain high refractive index and high Abbe number, inhibits glass material cost to rise, and the melting of glass can be improved Property, devitrification resistance, can also reduce the component of devitrification of glass ceiling temperature and specific gravity, but in formula of the invention, if its content More than 15%, then the chemical stability, devitrification resistance of glass reduce.It is therefore preferable that Y₂O₃Content range is 1-15%, more preferably Range is 3-15%, further preferably 6-10%.

Y₂O₃Glass refraction can be improved with other rare earth oxides, and because cost is compared with Gd₂O₃It is low, and glass can be reduced Glass density is conducive to lighting, and therefore, more having in the prior art introduces the component.However, in formula of the invention In system, Y₂O₃Content influence above-mentioned independently not only is generated on glass, it is also more with other multiple component synergic adjustment glass A performance.Including:

When optical glass of the invention contains Y₂O₃With La₂O₃When, it can more effectively improve the devitrification resistance of glass Can, and precise compression molding is easier to carry out when glass material makes glass elements, reduce the difficulty of glass elements manufacture；

Work as Y₂O₃/B₂O₃It when too low, is not easy that gas is discharged in fusion process, causes glass blister degree poor, therefore Y₂O₃/ B₂O₃Value lower limit be 0.15, preferably 0.2, more preferably 0.3；But Y₂O₃/B₂O₃Excessively high, glass has chemical stability to decline Trend, therefore, Y₂O₃/B₂O₃The value upper limit 2, preferably 1.8, more preferably 1.5, further preferably 1.3, further it is excellent It is selected as 1；

Gd₂O₃And Y₂O₃It can be replaced to a certain extent in terms of improving refractive index, Y₂O₃/Gd₂O₃Value it is higher, Cost of material is more advantageously reduced, in addition, inventor, which also found, works as Y₂O₃/Gd₂O₃Lower than 0.3 or when being higher than 3, it can all lead to glass The devitrification resistance of glass can deteriorate, therefore, by Y₂O₃/Gd₂O₃It is set as 0.3-3, preferably 0.5-2.5, more preferably higher than 1 but small In equal to 2；

Y₂O₃Accounting Y in all rare earth oxides₂O₃/Ln₂O₃There can be apparent adjust to make the devitrification resistance of glass With working as Y₂O₃/Ln₂O₃Value when being 0.08-0.45, devitrification resistance can be excellent, and preferred value is 0.1-0.4, further preferably For 0.1-0.3.

In addition, Y₂O₃/(SiO₂+B₂O₃) chemical stability that will affect glass, when the value is in 0.16-0.8, the change of glass Excellent in stability is learned, corrosion resistance is strong, can effectively extend the service life of optical instrument, more preferable Y₂O₃/(SiO₂+B₂O₃) Value be 0.2-0.7, further preferably 0.3-0.6.

Yb₂O₃It is high-refractivity and low-dispersion component, when content is more than 5%, stability, the devitrification resistance of glass are reduced, because This, Yb₂O₃Content range is limited to 0-5%.Simultaneously as Yb₂O₃Relative to Gd₂O₃、Y₂O₃More expensive, to glass melting Performance improvement effect is small, therefore does not preferably introduce.

RO belongs to alkaline earth oxide, is one of CaO, MgO, SrO and BaO or a variety of, is to appoint in the present invention The component of choosing.The Young's modulus that can promote glass is added in glass in proper amount of alkaline earth oxide, reduces the height of glass Warm viscosity, while glass ingredient is balanced, improve the meltdown property of glass.But when total content of RO is higher than 10%, excessively Alkaline earth oxide can reduce the devitrification resistance energy of glass.Therefore, the value of RO is set as 0-10% by the present invention, preferably 0-5%.

Rn₂O belongs to alkali metal oxide, is Li₂O、Na₂O、K₂One of O or a variety of is optional in the present invention Component.In glass system of the present invention, suitable alkali metal oxide can obtain expected high temperature viscosity, meanwhile, when appropriate Alkali metal oxide and B₂O₃When coexisting, B can also be improved₂O₃The consistency of network obtains better light transmission rate.It is very few Alkali metal oxide be unable to adjust the viscosity of glass to suitable range, and excessive alkali metal oxide can be destroyed sharply The devitrification resistance energy of glass.In the present invention, by Rn₂The value of O is set as 0-10%, preferably 0-5%.

In addition, can introduce the clarifying agent of 0-1%, preferably 0-0.5% in glass of the invention, these clarifying agents are optional Use Sb₂O₃Or/and CeO₂Or/and SnO₂。

In the range of not damaging glass performance of the invention, its a small amount of above-mentioned not referred to can be added as needed His ingredient, such as P₂O₅、Bi₂O₃、TeO₂、Ga₂O₃、GeO₂、Ta₂O₅、Lu₂O₃Deng.But V, Cr, Mn, Fe, Co, Ni, Cu, Ag and The transiting metal components such as Mo, even if glass is also subject to coloration, in visible light region in the case that independent or compound ground contains on a small quantity Specific wavelength generate absorption, to weaken the property of raising visible light transmittance effect of the invention, therefore, especially pair In the optical glass that the transmitance of visible light region wavelength requires, preferably do not include actually.

The compound of Pb, As, Th, Cd, Tl, Os, Be and Se have control to make as harmful chemical substance in recent years Tendency not only arranges environmental protection in the manufacturing process of glass, the disposition after manufacturing procedure and commercialization It is required for applying.Therefore, in the case where paying attention to the influence to environment, other than being inevitably mixed into, preferably actually Without containing them.Optical glass becomes the substance for not including pollution environment actually as a result,.Therefore, though do not take it is special Measure in environmental cure, optical glass of the invention are also able to carry out manufacture, processing and discard.

The performance of optical glass

[optical property]

Refractive index (nd) is tested according to GB/T7962.1-2010 method.

Abbe number (i.e. Abbe number, vd) is tested according to GB/T7962.1-2010 method.

[thermal property]

Thermal expansion coefficient (α_-30℃-70℃) tested according to GB/T7962.16-2010 method, unit 10^-7/K。

Transition temperature (T_g) measured by method as defined in GB/T 7962.16-2010, unit: DEG C.

Crystallization ceiling temperature test method are as follows: using the crystallization property of temperature gradient furnace method measurement glass, 180* is made in glass The sample of 10*10mm, side polishing are put into the furnace with temperature gradient (5 DEG C/cm) after being warming up to 1400 DEG C of heat preservations 4 hours Taking-up naturally cools to room temperature, observes devitrification of glass situation under the microscope, and glass the corresponding maximum temperature of crystal occurs and is The crystallization ceiling temperature of glass.The crystallization ceiling temperature of glass is lower, then stability is stronger at high temperature for glass, the technique of production Performance is better.

[chemical stability]

Water-fast effect stability (D_W) tested according to GB/T17129 method.

Acidproof effect stability (D_A) tested according to GB/T17129 method.

[bubble degree]

Bubble degree is tested according to GB/T7962.8-2010 method.

By test, glass of the invention is had the following performance: refractive index (nd) is 1.84-1.87, preferably 1.85- 1.86；Abbe number (vd) is 38-41, preferably 38.5-40；Thermal expansion coefficient (α_-30℃-70℃)≤75×10^-7/ K, preferably≤70 ×10^-7/K；Water-fast effect stability (D_W) reach 2 classes or more, preferably 1 class；Acidproof effect stability reaches 3 classes or more, excellent Choosing reaches 2 classes or more；Crystallization ceiling temperature is for 1250 DEG C hereinafter, preferably 1200 DEG C hereinafter, more preferably 1180 DEG C or less；Gas Bubble degree reaches A grades or more, preferably A₀Grade or more, more preferably A₀₀Grade；Glass transformation temperature (T_g) be 640 DEG C hereinafter, it is preferred that For 630 DEG C hereinafter, more preferably 625 DEG C or less.

Optical glass embodiment

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

The embodiment 1-48 of the table 1- table 6 and comparative example 1-5 of table 7 is by according to various embodiments or comparative example is corresponding Content weighing and hybrid optical glass is with common raw material (such as oxide, hydroxide, carbonate, nitrate), will mixing it is former Material is placed in platinum crucible, and 2-6h is melted in 1200-1500 DEG C, and after clarified, stirring and homogenizing, obtains homogeneous melt Glass casting mold and anneals this melten glass in mold.

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

The optical glass of the above embodiment of the present invention is easy to carry out precise compression molding, and devitrification resistance is good, Ln₂O₃Content Lower than 55%, cost is relatively low.Water-resistant stability (D_W) it is 2 classes or more, in preferred technical solution, D_WReach 1 class；It is acidproof steady Qualitative is 3 classes or more, in preferred technical solution, reaches 2 classes or more, chemical stability is good.Bubble degree at A grades or more, It is A in preferred technical solution₀Grade or more, in more preferably technical solution, reach A₀₀Grade, bubble degree are excellent.And it thermally expands Coefficient (α_-30℃-70℃)≤75×10^-7/ K, more preferably α_-30℃-70℃≤70×10^-7/ K is affected by temperature and expands or shrink Degree is low.Meanwhile also there is excellent devitrification resistance energy.

Gas preform embodiment

The obtained optical glass of embodiment 1-48 is cut into predefined size, then equably coated release on the surface Then agent is heated, softens, is press-formed, make recessed meniscus shaped lens, male bend moon-shaped lens, biconvex lens, concave-concave The prefabricated component of the various lens such as lens, plano-convex lens, plano-concave lens, prism.Or use the obtained optics of embodiment 1-48 Glass forms the preform of precision press formation, then precision press formation is processed into the shape of lens and prism, and production is pre- Product.

Optical element embodiment

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.Deployment can be also applied on the surface of obtained optical element Reflectance coating.

Optical instrument embodiment

By optical component 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, are used especially for automotive field Picture pick-up device and device.

Claims

1. optical glass, which is characterized in that in terms of weight %, contain: SiO₂: 0-10%, B₂O₃: 5-25%, ZrO₂: 0-15%, ZnO:10-25%, TiO₂+Nb₂O₅+WO₃: 2-30%, Ln₂O₃: 30-55%, the Ln₂O₃For La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃ Total content, wherein B₂O₃/Ln₂O₃For 0.3-0.8, Y₂O₃/Gd₂O₃For 0.3-3.

2. optical glass according to claim 1, it is characterised in that: also containing the RO of 0-10%, the Rn of 0-10%₂O, 0- 1% clarifying agent, the RO are one of MgO, CaO, SrO or BaO or a variety of, the Rn₂O is Li₂O、Na₂O、K₂In O One or more, the clarifying agent is Sb₂O₃、SnO₂、CeO₂One of or it is a variety of.

3. optical glass, which is characterized in that in terms of weight %, by the SiO of 0-10%₂, the B of 5-25%₂O₃, the ZrO of 0-15%₂, The TiO of the ZnO of 10-25%, 2-30%₂+Nb₂O₅+WO₃, the Ln of 30-55%₂O₃, the Rn of the RO of 0-10%, 0-10%₂O, 0- 1% clarifying agent composition, the Ln₂O₃For La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃Total content, the RO be MgO, CaO, SrO Or one of BaO or a variety of, the Rn₂O is Li₂O、Na₂O、K₂One of O or a variety of, the clarifying agent are Sb₂O₃、 SnO₂、CeO₂One of or a variety of, wherein B₂O₃/Ln₂O₃For 0.3-0.8, Y₂O₃/Gd₂O₃For 0.3-3.

4. optical glass according to claim 1 to 3, it is characterised in that: each component content meets following 4 kinds of situations One of or more than one:

1)SiO₂/(SiO₂+B₂O₃) it is 0-0.25；

2)Y₂O₃/Ln₂O₃For 0.08-0.45；

3)Y₂O₃/B₂O₃For 0.15-2；

4)Y₂O₃/(SiO₂+B₂O₃) it is 0.16-0.8.

5. optical glass according to claim 1 to 3, it is characterised in that: SiO₂: 1-8% and/or B₂O₃: 10- 23% and/or ZrO₂: 1-10% and/or ZnO:10-20% and/or TiO₂+Nb₂O₅+WO₃: 4-22% and/or Ln₂O₃: 35-52% and/or RO:0-5% and/or R₂O:0-5% and/or clarifying agent 0-0.5%.

6. optical glass according to claim 1 to 3, it is characterised in that: each component content meets following 6 kinds of situations One of or more than one:

1)SiO₂/(SiO₂+B₂O₃) it is 0.05-0.23；

2)Y₂O₃/Ln₂O₃For 0.1-0.4；

3)Y₂O₃/B₂O₃For 0.2-1.5；

4)Y₂O₃/(SiO₂+B₂O₃) it is 0.2-0.7；

5)B₂O₃/Ln₂O₃For 0.3-0.6；

6)Y₂O₃/Gd₂O₃For 0.5-2.5.

7. optical glass according to claim 1 to 3, it is characterised in that: SiO₂: 1-4% and/or B₂O₃: 15- 20% and/or ZrO₂: 2-6% and/or ZnO:13-17% and/or TiO₂+Nb₂O₅+WO₃: 10-18% and/or Ln₂O₃: 40-50%.

8. optical glass according to claim 1 to 3, it is characterised in that: each component content meets following 6 kinds of situations One of or more than one:

1)SiO₂/(SiO₂+B₂O₃) it is 0.08-0.2；

2)Y₂O₃/Ln₂O₃For 0.1-0.3；

3)Y₂O₃/B₂O₃For 0.3-1；

4)Y₂O₃/(SiO₂+B₂O₃) it is 0.3-0.6；

5)B₂O₃/Ln₂O₃For 0.3-0.5；

6)Y₂O₃/Gd₂O₃Greater than 1 but it is less than or equal to 2.

9. optical glass according to claim 1 to 3, it is characterised in that: Nb₂O₅: 1-15% and/or WO₃: 1- 15% and/or TiO₂: 0-10% and/or La₂O₃: 20-45% and/or Gd₂O₃: 0-15% and/or Y₂O₃: 1-15%, and/ Or Yb₂O₃: 0-5%.

10. optical glass according to claim 1 to 3, it is characterised in that: Nb₂O₅: 2-10% and/or WO₃: 2- 12% and/or TiO₂: 0-5% and/or La₂O₃: 25-40% and/or Gd₂O₃: 1-10% and/or Y₂O₃: 3-15%.

11. optical glass according to claim 1 to 3, it is characterised in that: Nb₂O₅: 4-8% and/or WO₃: 6- 10% and/or La₂O₃: 30-35% and/or Gd₂O₃: 3-7% and/or Y₂O₃: 6-10%, and/or be free of TiO₂。

12. optical glass according to claim 1 to 3, it is characterised in that: the refractive index (nd) of the optical glass For 1.84-1.87, preferably 1.85-1.86, Abbe number (vd) is 38.0-41.0, preferably 38.5-40.0.

13. optical glass according to claim 1 to 3, which is characterized in that it is steady that the optical glass powder method is water-fast Qualitative (D_W) it is 2 classes or more, preferably 1 class；Powder method acid-resistant stability (D_A) it is more than 3 classes, preferably 2 classes.

14. optical glass according to claim 1 to 3, which is characterized in that the thermal expansion coefficient of the optical glass (α_-30℃-70℃)≤75×10^-7/ K, preferably≤70 × 10^-7/K。

15. optical glass according to claim 1 to 3, which is characterized in that the bubble degree of the optical glass is A grades Or A grades or more, preferably A₀Grade or A₀Grade or more.

16. optical glass according to claim 1 to 3, which is characterized in that the transition temperature of the optical glass (Tg) for 640 DEG C hereinafter, preferably 630 DEG C hereinafter, more preferably 625 DEG C or less；The crystallization ceiling temperature of the optical glass For 1250 DEG C hereinafter, preferably 1200 DEG C hereinafter, more preferably 1180 DEG C or less.

17. gas preform is made of any optical glass of claim 1-16.

18. optical element is made of any optical glass of claim 1-16, or using described in claim 17 Gas preform be made.

19. optical instrument is made of the optical element described in claim 18.