CN109502964A

CN109502964A - Heavy-lanthanide flint glass and its prefabricated component, optical element and optical instrument

Info

Publication number: CN109502964A
Application number: CN201811493174.0A
Authority: CN
Inventors: 匡波
Original assignee: Chengdu Guangming Optoelectronics Co Ltd
Current assignee: Chengdu Guangming Optoelectronics Co Ltd
Priority date: 2018-12-07
Filing date: 2018-12-07
Publication date: 2019-03-22
Anticipated expiration: 2038-12-07
Also published as: JP2023134579A; JP2022510707A; WO2020114255A1; CN109502964B; JP7311603B2

Abstract

The invention discloses a kind of heavy-lanthanide flint glass and its prefabricated components, optical element and optical instrument.The heavy-lanthanide flint glass is contained: SiO in terms of weight %₂: 12-30%, Ln₂O₃: 10-25%, the Ln₂O₃For La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃Total content, TiO₂+Nb₂O₅+WO₃+Bi₂O₃: 10.5-40%, B₂O₃: 0-10%, RO:20-35%, the RO are one of BaO, CaO, MgO and SrO or a variety of, ZrO₂: 0.5-10%, wherein (SiO₂+TiO₂)/(B₂O₃+Nb₂O₅) it is 1-30.The refractive index (nd) of the glass is 1.86-1.92, Abbe number (vd) is 25-30, optical property needed for can satisfy precision instrument, and devitrification resistance energy is excellent, thermal refractive index coefficient is low, can effectively reduce thermal aberration caused by the temperature difference.

Description

Heavy-lanthanide flint glass and its prefabricated component, optical element and optical instrument

Technical field

The invention belongs to optical glass fields, and in particular to a kind of heavy-lanthanide flint glass and its prefabricated component, optical element and Optical instrument.

Background technique

Refractive index (nd) is 1.86-1.92, and Abbe number (vd) is that the heavy-lanthanide flint glass of 25-30 is widely used in precise light In the lens for learning instrument, these heavy-lanthanide flint glass can satisfy the requirement of modern precision die press technology for forming, but existing The thermal refractive index coefficient of heavy-lanthanide flint glass is higher.

The refractive index of optical glass is the function of temperature, the variation of refractive index caused by unit temperature, i.e. glass refraction Rate temperature coefficient, it is the critical performance parameters measuring temperature and influencing on the refractive index of optical glass, when temperature is raised, glass Expanded by heating reduces density, refractive index decline.

In the optical instrument used in the fields such as medical treatment, night photography, IC etching technology, optical lens makes It is constantly increased with environment temperature with using the time to increase, the refractive index of glass also changes greatly therewith, serious reduction glass Image quality, and then influence systemic resolution.It generally requires to be made up using thermal aberration compensation technique, such as the light of litho machine Object lens are carved to make up by movable lens combination, heat difference compensating element, etc., but these technical thresholds are higher, only by few in the world Number producer grasps, and greatlys restrict the popularization and application of the relevant technologies, is also unfavorable for forming market competition, breaks precision instrument valence The situation of lattice valuableness.

Moreover, existing heavy-lanthanide flint devitrification of glass ceiling temperature is higher, glass stability in high temperature process is poor, and heat adds Work technology difficulty is big, its use scope is caused to be restricted.

In addition, the heavy-lanthanide flint glass of current high density and brilliant idea coloration can not meet people, to pursue instrument and equipment light The requirement of miniaturization and high transmittance.

Therefore, it is necessary to develop, a kind of transmissivity is high, image quality is high, thermal refractive index coefficient is excellent, crystallization upper limit temperature Spend low heavy-lanthanide flint glass.

Summary of the invention

In view of the problems of the existing technology, the purpose of the present invention is to provide a kind of heavy-lanthanide flint glass, the glass Refractive index (nd) is 1.86-1.92, and Abbe number (vd) is 25-30, optical property needed for can satisfy precision instrument, Er Qiekang Crystallization property is excellent, thermal refractive index coefficient is low, can effectively reduce thermal aberration caused by the temperature difference.

The present invention still further provides prefabricated component, optical element and the optical instrument made by the heavy-lanthanide flint glass.

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

Heavy-lanthanide flint glass is contained in terms of weight %: SiO₂: 12-30%, Ln₂O₃: 10-25%, the Ln₂O₃For La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃Total content, TiO₂+Nb₂O₅+WO₃+Bi₂O₃: 10.5-40%, B₂O₃: 0-10%, RO: 20-35%, the RO are one of BaO, CaO, MgO and SrO or a variety of, ZrO₂: 0.5-10%, wherein (SiO₂+TiO₂)/ (B₂O₃+Nb₂O₅) it is 1-30.

Further, above-mentioned heavy-lanthanide flint glass is also contained in terms of weight %: Rn₂O:0-8%, the Rn₂O is Li₂O、Na₂O and K₂One of O or a variety of, Sb₂O₃: 0-1%, ZnO:0-7%, Ta₂O₅: 0-10%, Al₂O₃: 0-10%.

Heavy-lanthanide flint glass, in terms of weight %, by the SiO of 12-30%₂, the Ln of 10-25%₂O₃, the Ln₂O₃For La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃Total content, the TiO of 10.5-40%₂+Nb₂O₅+WO₃+Bi₂O₃, the RO of 20-35% is described RO is one of BaO, CaO, MgO and SrO or a variety of, the ZrO of 0.5-10%₂, the B of 0-10%₂O₃, the Rn of 0-8%₂O, institute State Rn₂O is Li₂O、Na₂O and K₂The Sb of one of O or a variety of, 0-1%₂O₃, the Ta of the ZnO of 0-7%, 0-10%₂O₅And 0- 10% Al₂O₃Composition, wherein (SiO₂+TiO₂)/(B₂O₃+Nb₂O₅) it is 1-30.

Further, heavy-lanthanide flint glass above-mentioned, each component content meet one of following 4 kinds of situations or it is a kind of with It is upper:

1)B₂O₃/TiO₂Greater than 0 and it is less than or equal to 1；

2)BaO/B₂O₃Greater than 0 and it is less than or equal to 70；

3)(La₂O₃+TiO₂+ZrO₂)/SiO₂For 0.7-6；

4)(SiO₂+La₂O₃+ZrO₂)/TiO₂For 0.75-6.5.

Further, heavy-lanthanide flint glass above-mentioned, in which: SiO₂: 15-25% and/or Ln₂O₃: 12-22%, and/or TiO₂+Nb₂O₅+WO₃+Bi₂O₃: 17-33% and/or RO:22-32% and/or ZrO₂: 2-8% and/or B₂O₃: 0.5-6%, And/or Rn₂O:0.5-6% and/or Sb₂O₃: 0-0.5% and/or ZnO:0-5% and/or Ta₂O₅: 0-5%, and/or Al₂O₃: 0-5%.

Further, heavy-lanthanide flint glass above-mentioned, each component content meet one of following 5 kinds of situations or it is a kind of with It is upper:

1)B₂O₃/TiO₂For 0.02-0.4；

2)BaO/B₂O₃For 3.6-64；

3)(La₂O₃+TiO₂+ZrO₂)/SiO₂For 1.2-5；

4)(SiO₂+La₂O₃+ZrO₂)/TiO₂For 1.1-3.7；

5)(SiO₂+TiO₂)/(B₂O₃+Nb₂O₅) it is 2.15-20.

Further, heavy-lanthanide flint glass above-mentioned, each component content meet one or both of following 2 kinds of situations:

6)SiO₂+TiO₂For 30-50%；

7)B₂O₃/SiO₂For 0.02-0.4.

Further, heavy-lanthanide flint glass above-mentioned, in which: SiO₂: 18-23% and/or Ln₂O₃: 13-18%, and/or TiO₂+Nb₂O₅+WO₃+Bi₂O₃: 22-31% and/or RO:23-30% and/or ZrO₂: 2-6% and/or B₂O₃: 1-4%, and/ Or Rn₂O:1-5% and/or Sb₂O₃: 0-0.2% and/or ZnO:0-3%, and/or be free of Ta₂O₅, and/or be free of Al₂O₃。

1)B₂O₃/TiO₂For 0.02-0.23；

2)BaO/B₂O₃For 5-30；

3)(La₂O₃+TiO₂+ZrO₂)/SiO₂For 1.5-4；

4)(SiO₂+La₂O₃+ZrO₂)/TiO₂For 1.2-2；

5)(SiO₂+TiO₂)/(B₂O₃+Nb₂O₅) it is 3.36-12.

6)SiO₂+TiO₂For 37-50%；

7)B₂O₃/SiO₂For 0.02-0.34.

Further, heavy-lanthanide flint glass above-mentioned, in which: TiO₂: 10-30% and/or Nb₂O₅: 0.5-10%；It is preferred that Ground, TiO₂: 15-25% and/or Nb₂O₅: 2-8%；More preferably, TiO₂: 19-24% and/or Nb₂O₅: 3-7%.

Further, heavy-lanthanide flint glass above-mentioned, in which: La₂O₃: 10-25% and/or BaO:20-35%, and/or Na₂O:0-8%；Preferably, La₂O₃: 12-22% and/or BaO:22-32% and/or Na₂O:0.5-6%；More preferably, La₂O₃: 13-18% and/or BaO:23-30% and/or Na₂O:1-5%.

Further, heavy-lanthanide flint glass above-mentioned, λ₇₀For 450nm hereinafter, preferably 440nm is hereinafter, more preferably 430nm or less；Its λ₅For 390nm hereinafter, preferably 385nm is hereinafter, more preferably 380nm or less；Density (ρ) is 4.5g/cm³ Hereinafter, preferably 4.3g/cm³Hereinafter, more preferably 4.25g/cm³Below；Crystallization ceiling temperature is 1200 DEG C hereinafter, preferably 1180 DEG C or less；Thermal refractive index coefficient is 2.4 × 10^-6/ DEG C hereinafter, preferably 2.3 × 10^-6/ DEG C or less.

Further, heavy-lanthanide flint glass above-mentioned, refractive index (nd) be 1.86-1.92, preferably 1.86-1.91, More preferably 1.87-1.90；Abbe number (vd) is 25-30, preferably 25-29, more preferably 26-29.

Further, heavy-lanthanide flint glass above-mentioned, transition temperature (T_g) be 720 DEG C hereinafter, preferably 710 DEG C with Under, more preferably 705 DEG C or less；Water-fast effect stability (D_W) it is 2 classes or more, preferably 1 class；Acidproof effect stability (D_A) More than 2 classes, preferably 1 class.Gas preform is made of heavy-lanthanide flint glass above-mentioned.

Optical element is made of heavy-lanthanide flint glass above-mentioned or gas preform.

Optical instrument is made of optical element above-mentioned.

The beneficial effects of the present invention are: by reasonable component proportion, make folding of the heavy-lanthanide flint glass needed for guaranteeing While penetrating rate and Abbe number, there is excellent thermal refractive index coefficient, crystallization ceiling temperature, λ₇₀、λ₅With chemical stability etc. Performance is suitble to promote and apply in requiring the precision instrument that transmissivity is high, image quality is high, thermal aberration is small.

Specific embodiment

Heavy-lanthanide flint glass

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

Heavy-lanthanide flint glass of the invention is contained in terms of weight %: SiO₂: 12-30%, Ln₂O₃: 10-25%, it is described Ln₂O₃For La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃Total content, TiO₂+Nb₂O₅+WO₃+Bi₂O₃: 10.5-40%, B₂O₃:0- 10%, RO:20-35%, the RO are one of BaO, CaO, MgO and SrO or a variety of, ZrO₂: 0.5-10%, wherein (SiO₂ +TiO₂)/(B₂O₃+Nb₂O₅) it is 1-30.

In glass of the present invention, SiO₂It is the Network former of glass, is the main component for constituting glass skeleton.SiO₂Contain It measures closely related with the devitrification resistance energy of glass, transmitance, refractive index and dispersion.If its content is lower than 12%, the refraction of glass Expected design is not achieved in rate and dispersion, while the devitrification resistance of glass can be with transmitance meeting sharp fall；If its content is higher than 30%, the solubility property of glass, devitrification resistance can decline, while expected design is not achieved in refractive index and dispersion.Therefore, at this In invention, SiO₂Content be set as 12-30%, preferably 15-25%, further preferably 18-23%.

B₂O₃It is also that glass network forms component, is optional component in the present invention.In some embodiments of the present invention In, introduce B₂O₃It can be improved glass fusible and devitrification resistance, but when its introduction volume is more than 10%, then glass is stablized at glass Property decline, and refractive index decline, therefore, B of the invention₂O₃Content be set as 0-10%, preferably 0.5-6%, further Preferably 1-4%.

SiO₂And B₂O₃As two kinds of glass network compositions, not only there is respective unique effect, but also mutually restricted influence glass At glass stability and glass transformation temperature (T_g), work as B₂O₃/SiO₂When ratio is higher than 0.4, glass transformation temperature (T_g) deterioration, and Work as B₂O₃/SiO₂When ratio is lower than 0.02, decline at glass stability.Therefore, contain B in some present invention₂O₃Heavy-lanthanide flint glass In glass embodiment, by B₂O₃/SiO₂Ratio is set as 0.02-0.4, more preferably 0.02-0.34.

Rare earth oxide Ln₂O₃(La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃) refractive index that helps to improve glass, when it always contains When amount is lower than 10%, expected optical constant can not be obtained, but when its total content is more than 25%, the chemical stability of glass, Devitrification resistance will reduce, and the cost of material that will improve glass.Therefore La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃Total content Ln₂O₃It is set as 10-25%, preferably 12-22%, further preferably 13-18%.In some embodiments, of the invention dilute It may include the La of 10-25% in native oxide₂O₃, the preferably La of 12-22%₂O₃, the La of more preferable 13-18%₂O₃, with further The refractive index for improving glass, improves the transmitance of visible light wave range, reduces the thermal refractive index coefficient of glass, improves devitrification resistance Energy.

Due to TiO₂、Nb₂O₅、WO₃、Bi₂O₃All have the function of improving refractive index but also improve dispersion, works as TiO₂+Nb₂O₅+ WO₃+Bi₂O₃Content is more than 40%, then glass dispersion is significantly raised, and glass coloration tendency increases, and transmitance can also reduce, therefore By TiO₂+Nb₂O₅+WO₃+Bi₂O₃The upper limit be set as 40%, the preferred upper limit is 33%, and the preferred upper limit is 31%.But Work as TiO₂+Nb₂O₅+WO₃+Bi₂O₃It is too low, and will lead to thermal stability and the decline of die mould performance of glass, therefore, its lower limit is set It is 10.5%, preferred lower limit is 17%, and more preferably lower limit is 22%.

In heavy-lanthanide flint glass of the invention, TiO is preferably used₂With Nb₂O₅Combination with obtain better refractive index and Ah Shellfish number.The TiO of 10% or more addition₂Into glass of the present invention, glass network can be participated in and formed, increased the anti-crystallization of glass and stablize Property, and can part fictitious hosts valuableness Nb₂O₅、WO₃、Bi₂O₃, but content is higher than 30% and will lead under glass transmitance Drop, glass coloration tendency increase；Nb₂O₅Be suitably introduced into glass can be made more stable, improve devitrification resistance, consider thus, this In the heavy-lanthanide flint glass of invention, by TiO₂Content be set as 10-30%, preferably 15-25%, more preferably 19-24%； By Nb₂O₅Content is set as 0.5-10%, preferably 2-8%, more preferably 3-7%.

Further, through inventor the study found that component B₂O₃And TiO₂Ratio B₂O₃/TiO₂It will affect the λ of glass₇₀、 λ₅, crystallization ceiling temperature and thermal refractive index coefficient, as ratio B₂O₃/TiO₂When greater than 1, crystallization ceiling temperature is increased, refractive index Temperature coefficient increases.From the purpose for obtaining the optical glass with excellent properties such as more high transmittances, the present invention is preferred B₂O₃/TiO₂Greater than 0 and it is less than or equal to 1, more preferable B₂O₃/TiO₂For 0.02-0.4, further preferred B₂O₃/TiO₂For 0.02- 0.23。

SiO₂And TiO₂Total content in whole form to the λ of glass₇₀、λ₅, water-fast effect stability (D_W) and it is acidproof Act on stability (D_A) have an important influence on, work as SiO₂+TiO₂Content be greater than 50% when, the transmission of the visible light region of glass Rate reduces, and coloring increases, water-fast effect stability (D_W) and acidproof effect stability (D_A) decline, but work as SiO₂+TiO₂Contain When amount is lower than 30%, glass increases at glass bad stability, thermal expansion coefficient.Therefore, in the present invention, it is preferred to SiO₂+TiO₂For 30-50%, more preferably 37-50%.

In addition, inventors have found that working as ratio (SiO₂+TiO₂)/(B₂O₃+Nb₂O₅) less than 1 when, stability, glass be deteriorated, analysis Brilliant ceiling temperature increases, and thermal refractive index coefficient increases, and thermal aberration is big, and specific gravity of glass increases, it is difficult to reach light-weighted mesh； But when the ratio is greater than 30, the decline of glass transmitance will lead to, coloring tendency obviously increases.Therefore, by ratio (SiO₂+ TiO₂)/(B₂O₃+Nb₂O₅) it is limited to 1-30, preferred ratio (SiO₂+TiO₂)/(B₂O₃+Nb₂O₅) it is 2.15-20, further Preferred ratio (SiO₂+TiO₂)/(B₂O₃+Nb₂O₅) it is 3.36-12.

RO belongs to alkaline earth oxide, is one of CaO, MgO, SrO and BaO or a variety of.In heavy lanthanum of the invention In flint glass, 20% or more alkaline earth oxide can promote the Young's modulus of glass, reduce the high temperature viscosity of glass, Glass ingredient is balanced simultaneously, improves the meltdown property of glass.But when total content of RO is higher than 35%, excessive alkaline earth Metal oxide can reduce the devitrification resistance energy of glass.Therefore, the value of RO is set as 20-35%, preferably 22- by the present invention 32%, more preferably 23-30%.It in some embodiments, may include 20-35%'s in alkaline earth oxide of the invention BaO, the preferably BaO of 22-32%, the BaO of more preferable 23-30% are improved with further decreasing the thermal refractive index coefficient of glass Glass devitrification resistance property and chemical stability.

In some embodiments, BaO and B₂O₃Adding proportion to glass refraction temperature coefficient, water-fast effect stablize Property (D_W) and acidproof effect stability (D_A) there is important influence.Work as BaO/B₂O₃When greater than 0, glass melting makes moderate progress, also It can reduce the thermal refractive index coefficient of glass, reduce thermal aberration, but work as BaO/B₂O₃When greater than 70, glass it is acidproof and water-fast Effect stability and devitrification resistance can decline.Therefore, by BaO/B₂O₃It is set greater than 0 and is less than or equal to 70, preferably BaO/ B₂O₃For 3.6-64, more preferable BaO/B₂O₃For 5-30.

ZrO₂It is essential component in the present invention, is a kind of high refractive low dispersive oxide, content is 0.5% or more ZrO₂ Addition glass in can promote the refractive index of glass and adjust dispersion.Meanwhile devitrification resistance energy and the change of glass can be promoted Learn stability.But in heavy-lanthanide flint glass of the invention, if its content is higher than 10%, glass can become difficult to melt, and melt Refining temperature can rise, and inside glass is easy to cause field trash and its transmitance decline occur.Therefore, content is set as 0.5- 10%, preferably 2-8%, further preferably 3-7%.

ZrO₂In glass of the invention with component La₂O₃、SiO₂、TiO₂Common nd, vd, λ for adjusting glass₇₀、λ₅, and The performances such as crystallization ceiling temperature and thermal refractive index coefficient.Through inventor's experimental verification, when with ratio (La₂O₃+TiO₂+ZrO₂)/ SiO₂Adjust nd, vd, λ₇₀、λ₅When, preferred ratio range is 0.7-6, and when the value is less than 0.7, glass melting is deteriorated, and is stablized Property be deteriorated, refractive index decline；And work as (La₂O₃+TiO₂+ZrO₂)/SiO₂When higher than 6, the transmitance of glass visible light region is reduced, Degree of staining is deteriorated.More preferably (La₂O₃+TiO₂+ZrO₂)/SiO₂Ratio range be 1.2-5, most preferred ratio range is 1.5- 4.When with ratio (SiO₂+La₂O₃+ZrO₂)/TiO₂Adjust the λ of glass₇₀、λ₅, crystallization ceiling temperature and when thermal refractive index coefficient, Preferred ratio range is 0.75-6.5, when which is 6.5 or less, can obtain superior optical transmittance and more preferably resist Crystallization property；But when the value is less than 0.75 or is greater than 6.5, it may be difficult to thermal refractive index coefficient be made to be maintained at 2.4 × 10^-6/ DEG C hereinafter, optical property and devitrification resistance can obviously be deteriorated.Scheme more preferably, ratio (SiO₂+La₂O₃+ZrO₂)/ TiO₂Range be 1.1-3.7, most preferred range is 1.2-2.

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.But Excessive alkali metal oxide can sharply destroy the devitrification resistance energy of glass again.Therefore, in the present invention, by Rn₂The value of O is set For 0-8%, preferably 0.5-6%, more preferably 1-5%.It in some embodiments, can in alkali metal oxide of the invention Na comprising 0-8%₂O, the preferably Na of 0.5-6%₂O, the Na of more preferable 1-5%₂O further decreases the transition temperature of glass, Improve the melting behaviour of glass.

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.In glass system of the present invention, ZnO is optional component, content For 0-7%, preferably 0-5%, more preferably 0-3%.

Ta₂O₅It can play the role of increasing refractive index reduction dispersion, be optional in heavy-lanthanide flint glass of the invention Component, content 0-10%, preferably 0-5%.Because it is expensive, therefore Ta is not contained more preferably₂O₅。

Al₂O₃The thermal expansion coefficient that glass can be reduced improves the thermal stability of glass.But high Al₂O₃Concentration is usual Reduce the liquidus viscosity of glass.In the present invention, its content is set as 0-10%, preferably 0-5%, do not contained more preferably Al₂O₃。

In addition, the clarifying agent Sb of 0-1%, preferably 0-0.5% can be introduced in heavy-lanthanide flint glass of the invention₂O₃。

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、TeO₂、GeO₂、Lu₂O₃Deng.But the transiting metal components such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo, Even if glass is also subject to coloration in the case that independent or compound ground contains on a small quantity, the specific wavelength in visible light region is generated It absorbs, to weaken the property of raising visible light transmittance effect of the invention, therefore it is desirable, especially for visible light region wavelength The optical glass that requires of transmitance, 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.

" do not include " " not containing " " 0% " documented by the present invention to refer to not deliberately by the compound, molecule or element It is added in heavy-lanthanide flint glass of the present invention Deng as raw material；But as the raw material and/or equipment of production glass, there can be certain It is not the impurity deliberately added or component a bit, a small amount of or trace can contains in final heavy-lanthanide flint glass, such situation In the scope of protection of the patent of the present invention.

As described above, a kind of group of branch has an impact multiple performances of glass in glass system of the invention. Same component may bring the deterioration of another performance, thus the mutual collaboration and phase of various ingredients while optimization to a certain performance Mutually restricting just is particularly important in entire glass system.The heavy-lanthanide flint glass that the present inventor obtains through experimental study Glass is in nd, vd, λ₇₀、λ₅, ρ, crystallization ceiling temperature, thermal refractive index coefficient, D_W、D_A, at glass stability or transition temperature (T_g) etc. Aspect has excellent performance.

The performance indexes of heavy-lanthanide flint glass of the present invention or its product is tested using following methods:

[refractive index]

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

[abbe number]

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

[coloring of glass]

λ₇₀Refer to that glass transmittance reaches corresponding wavelength when 70%, λ 5 refers to that glass transmittance reaches corresponding when 5% Wavelength.Wherein, λ₇₀Measurement be using with two parallel to each other and optical polish opposite planes with a thickness of 10 ± 0.1mm Glass, measure the spectral transmission in wavelength domain from 280nm to 700nm and show the wavelength of transmissivity 70%.

[thermal refractive index coefficient]

Thermal refractive index coefficient is tested according to 7962.4-2010 prescriptive procedure of GB/T, the refractive index of 20~40 DEG C of measurement Temperature coefficient.

[transition temperature of glass]

Transition temperature (the T of glass_g) measured by method as defined in GB/T7962.16-2010, unit: DEG C.

[crystallization ceiling temperature]

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.

[density]

Density (ρ) is tested according to " GB/T 7962.20-1987 colouless optical glass test method density measurement method ".

By test, heavy-lanthanide flint glass of the invention is had the following performance: refractive index (nd) is 1.86-1.92, preferably For 1.86-1.91, more preferably 1.87-1.90；Abbe number (vd) is 25-30, preferably 25-29, more preferably 26-29；Turn Temperature (T_g) be 720 DEG C hereinafter, preferably 710 DEG C hereinafter, more preferably 705 DEG C or less；λ₇₀For 450nm hereinafter, preferably 440nm is hereinafter, more preferably 430nm or less；λ₅For 390nm hereinafter, preferably 385nm is hereinafter, more preferably 380nm or less； Density (ρ) is 4.5g/cm³Hereinafter, preferably 4.3g/cm³Hereinafter, more preferably 4.25g/cm³Below；Water-fast effect stability (D_W) it is 2 classes or more, preferably 1 class；Acidproof effect stability (D_A) it is 2 classes or more, preferably 1 class；Crystallization ceiling temperature is 1200 DEG C hereinafter, preferably 1180 DEG C or less；Thermal refractive index coefficient is 2.4 × 10^-6/ DEG C hereinafter, preferably 2.3 × 10^-6/ DEG C or less.

In the following, gas preform, optical element and optical instrument that description is of the invention.

Gas preform and optical element of the invention is formed by the heavy-lanthanide flint glass of aforementioned present invention.Of the invention Gas preform has high refractive index and lower thermal refractive index coefficient characteristic；Optical element of the invention have high refractive index and Lower thermal refractive index coefficient characteristic 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.

In addition, since refractive index is relatively high, through combination in camera optical system, leading to for prism Bending optical path is crossed, towards required direction, compact, wide-angle optics system can be realized.

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 of heavy-lanthanide flint glass]

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

Glass in order to obtain with composition shown in 1~table of table 6, uses carbonate, nitrate, hydroxide, oxidation Object, boric acid etc. are used as raw material, and raw material corresponding to optical glass element is weighed each raw material in proportion, become after being sufficiently mixed and adjust Raw material is closed, which is put into platinum crucible, is heated to 1200~1450 DEG C, is formed after fusing, stirring, clarification Uniform melten glass, then will be poured into the mold of preheating after the melten glass moderately cooling and keep 2 at 650~700 DEG C Slow cooling is carried out after~4 hours, obtains optical glass.In addition, the test method measures the spy of each glass through the invention Property, and measurement result is indicated in 1~table of table 6.

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

[gas preform embodiment]

By the obtained heavy-lanthanide flint glass-cutting of embodiment 1-36 at predefined size, then equably coating is de- on the surface Then mould agent is heated, softens, is press-formed, make recessed meniscus shaped lens, male bend moon-shaped lens, biconvex lens, double The prefabricated component of the various lens such as concavees lens, plano-convex lens, plano-concave lens, prism.Or it is obtained heavy using embodiment 1-36 Lanthanum flint glass forms the preform of precision press formation, then precision press formation is processed into the shape of lens and prism, Make prefabricated component.

[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.It can also Tu Bufang on the surface of obtained optical element Reflectance coating.

[optical instrument embodiment]

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

Claims

1. heavy-lanthanide flint glass, which is characterized in that in terms of weight %, contain: SiO₂: 12-30%, Ln₂O₃: 10-25%, it is described Ln₂O₃For La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃Total content, TiO₂+Nb₂O₅+WO₃+Bi₂O₃: 10.5-40%, B₂O₃: 0- 10%, RO:20-35%, the RO are one of BaO, CaO, MgO and SrO or a variety of, ZrO₂: 0.5-10%, wherein (SiO₂ +TiO₂)/(B₂O₃+Nb₂O₅) it is 1-30.

2. heavy-lanthanide flint glass according to claim 1, which is characterized in that in terms of weight %, also contain: Rn₂O:0-8%, The Rn₂O is Li₂O、Na₂O and K₂One of O or a variety of, Sb₂O₃: 0-1%, ZnO:0-7%, Ta₂O₅: 0-10%, Al₂O₃: 0-10%.

3. heavy-lanthanide flint glass, which is characterized in that in terms of weight %, by the SiO of 12-30%₂, the Ln of 10-25%₂O₃, described Ln₂O₃For La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃Total content, the TiO of 10.5-40%₂+Nb₂O₅+WO₃+Bi₂O₃, 20-35%'s RO, the RO are one of BaO, CaO, MgO and SrO or a variety of, the ZrO of 0.5-10%₂, the B of 0-10%₂O₃, 0-8%'s Rn₂O, the Rn₂O is Li₂O、Na₂O and K₂The Sb of one of O or a variety of, 0-1%₂O₃, the ZnO of 0-7%, 0-10%'s Ta₂O₅And the Al of 0-10%₂O₃Composition, wherein (SiO₂+TiO₂)/(B₂O₃+Nb₂O₅) it is 1-30.

4. heavy-lanthanide flint glass according to claim 1 to 3, which is characterized in that each component content meets following One of 4 kinds of situations or more than one:

1)B₂O₃/TiO₂Greater than 0 and it is less than or equal to 1；

2)BaO/B₂O₃Greater than 0 and it is less than or equal to 70；

3)(La₂O₃+TiO₂+ZrO₂)/SiO₂For 0.7-6；

4)(SiO₂+La₂O₃+ZrO₂)/TiO₂For 0.75-6.5.

5. heavy-lanthanide flint glass according to claim 1 to 3, it is characterised in that: SiO₂: 15-25%, and/or Ln₂O₃: 12-22% and/or TiO₂+Nb₂O₅+WO₃+Bi₂O₃: 17-33% and/or RO:22-32% and/or ZrO₂: 2-8%, And/or B₂O₃: 0.5-6% and/or Rn₂O:0.5-6% and/or Sb₂O₃: 0-0.5% and/or ZnO:0-5%, and/or Ta₂O₅: 0-5% and/or Al₂O₃: 0-5%.

6. heavy-lanthanide flint glass according to claim 1 to 3, which is characterized in that each component content meets following One of 5 kinds of situations or more than one:

1)B₂O₃/TiO₂For 0.02-0.4；

2)BaO/B₂O₃For 3.6-64；

3)(La₂O₃+TiO₂+ZrO₂)/SiO₂For 1.2-5；

4)(SiO₂+La₂O₃+ZrO₂)/TiO₂For 1.1-3.7；

5)(SiO₂+TiO₂)/(B₂O₃+Nb₂O₅) it is 2.15-20.

7. heavy-lanthanide flint glass according to claim 1 to 3, it is characterised in that: SiO₂: 18-23%, and/or Ln₂O₃: 13-18% and/or TiO₂+Nb₂O₅+WO₃+Bi₂O₃: 22-31% and/or RO:23-30% and/or ZrO₂: 2-6%, And/or B₂O₃: 1-4% and/or Rn₂O:1-5% and/or Sb₂O₃: 0-0.2% and/or ZnO:0-3%, and/or be free of Ta₂O₅, and/or be free of Al₂O₃。

8. heavy-lanthanide flint glass according to claim 1 to 3, which is characterized in that each component content meets following One of 5 kinds of situations or more than one:

1)B₂O₃/TiO₂For 0.02-0.23；

2)BaO/B₂O₃For 5-30；

3)(La₂O₃+TiO₂+ZrO₂)/SiO₂For 1.5-4；

4)(SiO₂+La₂O₃+ZrO₂)/TiO₂For 1.2-2.0；

5)(SiO₂+TiO₂)/(B₂O₃+Nb₂O₅) it is 3.36-12.00.

9. heavy-lanthanide flint glass according to claim 1 to 3, it is characterised in that: TiO₂: 10-30%, and/or Nb₂O₅: 0.5-10%；Preferably, TiO₂: 15-25% and/or Nb₂O₅: 2-8%；More preferably, TiO₂: 19-24%, and/or Nb₂O₅: 3-7%.

10. heavy-lanthanide flint glass according to claim 1 to 3, it is characterised in that: La₂O₃: 10-25%, and/ Or BaO:20-35% and/or Na₂O:0-8%；Preferably, La₂O₃: 12-22% and/or BaO:22-32% and/or Na₂O: 0.5-6%；More preferably, La₂O₃: 13-18% and/or BaO:23-30% and/or Na₂O:1-5%.

11. heavy-lanthanide flint glass according to claim 1 to 3, which is characterized in that the λ of the glass₇₀For 450nm hereinafter, preferably 440nm hereinafter, more preferably 430nm or less；λ₅For 390nm hereinafter, preferably 385nm is hereinafter, more Preferably 380nm or less；The density (ρ) of the glass is 4.5g/cm³Hereinafter, preferably 4.3g/cm³Hereinafter, more preferably 4.25g/cm³Below；The crystallization ceiling temperature of the glass is 1200 DEG C hereinafter, preferably 1180 DEG C or less；The glass Thermal refractive index coefficient is 2.4 × 10^-6/ DEG C hereinafter, preferably 2.3 × 10^-6/ DEG C or less.

12. heavy-lanthanide flint glass according to claim 1 to 3, which is characterized in that the refractive index of the glass It (nd) is 1.86-1.92, preferably 1.86-1.91, more preferably 1.87-1.90；Abbe number (vd) is 25-30, preferably 25- 29, more preferably 26-29.

13. heavy-lanthanide flint glass according to claim 1 to 3, which is characterized in that the transformation temperature of the glass Spend (T_g) be 720 DEG C hereinafter, preferably 710 DEG C hereinafter, more preferably 705 DEG C or less；The water-fast effect stability of the glass (D_W) it is 2 classes or more, preferably 1 class；Acidproof effect stability (D_A) it is 2 classes or more, preferably 1 class.

14. gas preform is made of any heavy-lanthanide flint glass of claim 1-13.

15. optical element is made of any heavy-lanthanide flint glass of claim 1-13, or uses claim 14 The gas preform is made.

16. optical instrument is made of the optical element described in claim 15.