CN107879620A

CN107879620A - Optical glass, gas preform and optical element

Info

Publication number: CN107879620A
Application number: CN201610861598.2A
Authority: CN
Inventors: 匡波
Original assignee: Chengdu Guangming Optoelectronics Co Ltd
Current assignee: CDGM Glass Co Ltd; Chengdu Guangming Optoelectronics Co Ltd
Priority date: 2016-09-29
Filing date: 2016-09-29
Publication date: 2018-04-06
Anticipated expiration: 2036-09-29
Also published as: JP2018052801A; CN107879620B; JP6632156B2

Abstract

The present invention provides the high-refraction low-dispersion optical glass for mold that a kind of cost is low, refractive index is 1.77 1.85, Abbe number is 40 48.Optical glass, its refractive index are 1.77 1.85, and Abbe number is 40 48, and its composition represents by weight percentage, contains：SiO₂+B₂O₃：15 40%；La₂O₃+Gd₂O₃+Y₂O₃：35 70%；WO₃+Nb₂O₅+ZrO₂+TiO₂：1 30%；ZnO：11 30%；Nb₂O₅/Gd₂O₃For 0.01 0.45.The present invention reduces Ta₂O₅Content, optimize cost of material；Designed by rational component, the optical glass of the present invention is beneficial to accurate die pressing while required optical constant is realized, and there is excellent chemical stability, and the gas preform and optical element formed by the optical glass.

Description

Optical glass, gas preform and optical element

Technical field

The present invention relates to a kind of high-refraction low-dispersion optical glass for mold, more particularly, to a kind of inexpensive high refractive low dispersive Optical glass and optical element.

Background technology

In recent years, with the digitlization of optical system and developing rapidly for high-precision densification, taken the photograph in digital camera, video camera etc. In the optical devices such as the image player such as shadow equipment and projecting apparatus, projection TV (projection) equipment, make to reducing in optical system The number of the optical elements such as lens, prism, make the requirement more and more higher of the lightweight of optical system entirety and miniaturization.In light In the design of system, the glass of widely used high index of refraction or miniaturization, ultrathin and wide are realized using non-spherical lens Angling, it is easier to realize the correction of aberration while optical system lightweight high performance is realized, therefore, high refractive low dispersive The research and development demand of glass is just gradually increased.

Early stage makes high refractive low dispersive glass and all contains substantial amounts of Ta₂O₅, a kind of refractive index as disclosed in CN1876589A 1.75-1.85, Abbe number 34-44 optical glass, wherein just contain more than 15% but less than 35% Ta₂O₅.Tantalum is one Kind scarcity metals, Ta₂O₅Control of the use to product cost it is extremely disadvantageous, therefore dropped in high refractive low dispersive glass composition It is low or without using Ta₂O₅, into the R＆D target of optical glass R＆D worker.

The content of the invention

The technical problems to be solved by the invention are to provide a kind of low cost, refractive index 1.77-1.85, Abbe number 40-48 high-refraction low-dispersion optical glass for mold.

The present invention also provides a kind of gas preform and optical element formed by above-mentioned optical glass.

The technical proposal for solving the technical problem of the invention is：Optical glass, its refractive index (nd) are 1.77- 1.85, Abbe number (vd) is 40-48, and its composition represents by weight percentage, contains：SiO₂+B₂O₃：15-40%；La₂O₃+ Gd₂O₃+Y₂O₃：35-70%；WO₃+Nb₂O₅+ZrO₂+TiO₂：1-30%；ZnO：11-30%；Nb₂O₅/Gd₂O₃For 0.01-0.45.

Further, its composition represents by weight percentage, also contains：Al₂O₃：0-10%；Ta₂O₅：0-8%；Rn₂O：0- 10%, wherein Rn₂O is Li₂O、Na₂O、K₂One or more in O；RO：0-10%, wherein RO are MgO, CaO, SrO or BaO In one or more.

Further, SiO₂+B₂O₃：18-38%；And/or La₂O₃+Gd₂O₃+Y₂O₃：35-65%；And/or WO₃+Nb₂O₅+ ZrO₂+TiO₂：2-20%；Rn₂O：0-5%, wherein Rn₂O is Li₂O、Na₂O、K₂One or more in O；RO：0-5%, wherein RO is the one or more in MgO, CaO, SrO or BaO.

Further, SiO₂+B₂O₃：20-35%；And/or La₂O₃+Gd₂O₃+Y₂O₃：38-60%；And/or WO₃+Nb₂O₅+ ZrO₂+TiO₂：4-15%；Rn₂O：0-2%, wherein Rn₂O is Li₂O、Na₂O、K₂One or more in O；RO：0-1%, wherein RO is the one or more in MgO, CaO, SrO or BaO.

Further, the content of each component meets the one or more in following 9 kinds of conditions：

1)Ta₂O₅/Nb₂O₅：Less than 1；

2)ZnO/(SiO₂+B₂O₃) it is 0.3-2；

3)Gd₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) it is 0.2-0.55；

4)SiO₂/(SiO₂+B₂O₃) it is 0.2-0.6；

5)Nb₂O₅/Gd₂O₃For 0.01-0.4；

6)(WO₃+Ta₂O₅+Nb₂O₅)/(ZrO₂+TiO₂) it is 0.1-5；

7)Nb₂O₅/ ZnO is 0.01-0.5；

8)TiO₂/(TiO₂+Nb₂O₅) it is 0.01-0.8；

9)ZnO/(WO₃+Ta₂O₅+Nb₂O₅+TiO₂) it is more than 1.8.

Further, wherein：Nb₂O₅+ZrO₂+TiO₂：1-25%.

Further, wherein：Nb₂O₅：More than 0 but less than or equal to 8%；ZrO₂：More than 0 but less than or equal to 15%； TiO₂：0-8%；WO₃：0-15%.

Further, wherein：La₂O₃：20-40%；Gd₂O₃：11-30%；Y₂O₃：0-15%.

Further, wherein：SiO₂：4-20%；B₂O₃：8-24%；Li₂O：0-2%；Na₂O：0-10%；K₂O：0- 10%.

Further, wherein：SiO₂：5-18%；And/or B₂O₃：10-23%；And/or La₂O₃：20-35%；And/or Gd₂O₃：11-25%；And/or Y₂O₃：0-10%；And/or WO₃：0-10%；And/or Ta₂O₅：0-5%；And/or Nb₂O₅：0.1- 6%；And/or ZrO₂：1-10%；And/or ZnO：15-30%；And/or TiO₂：0-5；And/or Al₂O₃：0-5%；And/or Li₂O： 0-1%；And/or Na₂O：0-5%；And/or K₂O：0-5%；And/or Sb₂O₃：0-0.5%；And/or RO：0-5%, wherein, RO For the one or more in MgO, CaO, SrO or BaO.

Further, wherein：SiO₂：6-15%；And/or B₂O₃：12-20%；And/or La₂O₃：22-32%；And/or Gd₂O₃：12-22%；And/or Y₂O₃：0-8%；And/or WO₃：0-7%；And/or ZrO₂：2-8%；And/or ZnO：15-25%； And/or TiO₂：0-2%.

Further, wherein：Ta₂O₅/Nb₂O₅：Less than 0.8；And/or ZnO/ (SiO₂+B₂O₃) it is 0.5-1.8；And/or Gd₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) it is 0.25-0.5；And/or SiO₂/(SiO₂+B₂O₃) it is 0.23-0.5；And/or Nb₂O₅/ Gd₂O₃For 0.02-0.35；And/or (WO₃+Ta₂O₅+Nb₂O₅)/(ZrO₂+TiO₂) it is 0.1-3；And/or Nb₂O₅/ ZnO is 0.02- 0.35；And/or TiO₂/(TiO₂+Nb₂O₅) it is 0.05-0.7；And/or ZnO/ (WO₃+Ta₂O₅+Nb₂O₅+TiO₂) it is 3-15.

Further, wherein：Ta₂O₅/Nb₂O₅：Less than 0.5；ZnO/(SiO₂+B₂O₃) it is 0.5-1.45；And/or Gd₂O₃/ (La₂O₃+Gd₂O₃+Y₂O₃) it is 0.25-0.45；And/or SiO₂/(SiO₂+B₂O₃) it is 0.25-0.45；And/or Nb₂O₅/Gd₂O₃For 0.05-0.25；And/or (WO₃+Ta₂O₅+Nb₂O₅)/(ZrO₂+TiO₂) it is 0.1-1；And/or Nb₂O₅/ ZnO is 0.03-0.25； And/or TiO₂/(TiO₂+Nb₂O₅) it is 0.1-0.6；And/or ZnO/ (WO₃+Ta₂O₅+Nb₂O₅+TiO₂) it is 4-12.

Further, wherein：Nb₂O₅+ZrO₂+TiO₂：2-20%；La₂O₃+Gd₂O₃+Y₂O₃：40-55%.

Further, wherein：Nb₂O₅+ZrO₂+TiO₂：4-15%.

Further, wherein：SiO₂、B₂O₃、La₂O₃、Gd₂O₃、Y₂O₃、TiO₂、Nb₂O₅、WO₃、ZrO₂Total with ZnO contains Measure as more than 95%, and be free of Ta₂O₅。

Further, wherein：SiO₂、B₂O₃、La₂O₃、Gd₂O₃、Y₂O₃、TiO₂、Nb₂O₅、ZrO₂Total content with ZnO is More than 99%.

Further, its composition represents by weight percentage, contains：

Yb₂O₃：0-10%；

P₂O₅：0-10%；

Bi₂O₃：0-10%；

TeO₂：0-10%；

Ga₂O₃:0-10%；

Lu₂O₃:0-10%；

GeO₂：0-8%；

CeO₂：0-1%；

SnO₂：0-1%；

Sb₂O₃：0-1%；

F：0-10%.

Further, its composition represents by weight percentage, contains：

Yb₂O₃：0-5%；

P₂O₅：0-5%；

Bi₂O₃：0-5%；

TeO₂：0-5%；

Ga₂O₃:0-5%；

Lu₂O₃:0-5%；

GeO₂：0-5%；

CeO₂：0-0.5%；

SnO₂：0-0.5%；

Sb₂O₃：0-1%；

F：0-5%.

Further, the transmittance of glass reaches corresponding wavelength X when 80%₈₀For below 410nm, transmittance reaches 5% When corresponding wavelength X₅For below 350nm；Crystallization ceiling temperature is below 1160 DEG C；Glass transformation temperature (Tg) be 630 DEG C with Under；The density (ρ) of glass is 5.00g/cm³Below.

Further, the transmittance of glass reaches corresponding wavelength X when 80%₈₀For below 400nm, transmittance reaches 5% When corresponding wavelength X₅For below 340nm；Crystallization ceiling temperature is below 1150 DEG C；Glass transformation temperature (Tg) be 620 DEG C with Under；The density (ρ) of glass is 4.90g/cm³Below

Gas preform, it is made of above-mentioned optical glass.

Optical element, it is made of above-mentioned optical glass.

The beneficial effects of the invention are as follows：Reduce Ta₂O₅Content, optimize cost of material；Designed by rational component, The optical glass of the present invention is beneficial to accurate die pressing while required optical constant is realized, and there is excellent chemically stable Property, and the gas preform and optical element formed by the optical glass.

Embodiment

Ith, optical glass

Optical glass of the present invention is based on considering reducing cost of material, reduces and do not contain expensive Ta even₂O₅Contain Amount, it is 1.77-1.85 to obtain refractive index, and Abbe number is 40-48 Spectralite with high refractivity and low dispersion.

The composition of the optical glass of the present invention is described in detail below, the content of each glass ingredient, total content do not have such as There is special instruction, be then all indicated using percentage by weight.In addition, in the following description, mention below setting or advise When more than definite value, also including the setting.

B₂O₃It is that glass network forms component, has and improve glass fusible and devitrification resistance, reduce glass transition temperature With the effect of density, in order to reach the effect above, present invention introduces more than 8% or more B₂O₃, it is preferably introduced into more than 10% B₂O₃, the more preferably B of introducing more than 12%₂O₃；But when its introduction volume is more than 24%, then stability, glass declines, and reflects Rate declines, and can not obtain the high index of refraction of the present invention, therefore, B of the invention₂O₃Content be set to the upper limit, preferred upper limit by 24% For 23%, more preferably the upper limit is 20%.

SiO₂And glass former, with B₂O₃The loose chain multi-layered network formed is different, SiO₂Shape in glass Into be silicon-oxy tetrahedron three-dimensional network, it is very fine and close firm.Such network is added in glass, to loose boron oxygen triangle Body [BO₃] network reinforced, it is become fine and close, so as to lift the high temperature viscosity of glass, at the same time, silicon-oxy tetrahedron three The ability enhancing of the crystallization cation such as the addition of network, glass network isolation La, Nb, Li is tieed up, adds crystallization threshold value so that glass The devitrification resistance of glass can be lifted, SiO in glass of the present invention₂The lower limit of content is 4%, preferably 5%, when more preferably 6% on It is preferable to state effect；If but SiO₂Content it is excessive, can raise the transition temperature of glass, and reduce the meltbility of glass, because This its upper content limit is 20%, preferred upper limit 18%, and the further preferred upper limit is 15%.

B₂O₃And SiO₂All it is that glass network forms component, when its total content is less than 15%, crystallization trend increase can not The glass stablized；When its total content is more than 40%, the optical constant of glass can be less than design load.Therefore, B₂O₃And SiO₂ Total content (B₂O₃+SiO₂) it is 15-40%, preferably 18-38%, more preferably 20-35%.In addition, the present invention passes through control SiO₂Content and SiO₂And B₂O₃Total content ratio SiO₂/(SiO₂+B₂O₃) in 0.2-0.6, it can not only ensure glass The meltbility of glass, while stability, glass and high temperature viscosity can be effectively increased, especially as its SiO₂/(SiO₂+B₂O₃) value is During 0.23-0.5, while glass high refraction and low dispersion optical characteristic and low transition temperature characteristic is maintained, can effectively it change The devitrification resistance energy of kind glass, more preferably 0.25-0.45.

In the present invention, La₂O₃、Gd₂O₃、Y₂O₃The refractive index of glass can be improved, when its total content is less than 35%, Expected optical constant can not be obtained, when its total content is more than 70%, stability, the devitrification resistance of glass reduce, therefore La₂O₃、Gd₂O₃、Y₂O₃Total content (La₂O₃+Gd₂O₃+Y₂O₃) it is 35-70%, preferably 35-65%, more preferably 38- 60%, it is still more preferably 40-55%.

La₂O₃It is the necessary component for obtaining optical characteristics needed for 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 During less than 20%, it is difficult to realize required optical characteristics；But when its content is more than 40%, glass devitrification resistance and meltbility Can it deteriorate.Therefore, La of the invention₂O₃Content be 20-40%, preferred scope 20-35%, preferred scope is 22- 32%.

Gd₂O₃Can increase the dispersion that the refractive index of glass and unobvious improve glass, in the present invention by introduce 11% with On Gd₂O₃With La₂O₃Coexist, the stability to form glass can be improved, and significantly increase the chemical stability of glass, While refractive index is maintained, the excessive rising of Abbe number is controlled；If its content is more than 30%, glass devitrification resistance drop Low and glass density is in rising trend.Therefore, Gd of the invention₂O₃Content be 11-30%, preferred scope 11-25%, More preferably scope is 12-22%.

The component of the high refractive low dispersive effect of the present invention preferably also introduces Y₂O₃, it is maintaining high index of refraction and high Abbe number While, suppress glass material cost increase, and the meltbility of glass, devitrification resistance can be improved, it can also reduce on devitrification of glass Limit temperature and proportion, if but its content more than 15%, stability, the devitrification resistance of glass reduce.Therefore, Y₂O₃Content range For 0-15%, more preferably preferred scope 0-10%, 0-8%.

Make La in the present invention₂O₃And Gd₂O₃Coexist；Or preferably make La₂O₃、Gd₂O₃And Y₂O₃Coexist；More preferably Gd₂O₃/ (La₂O₃+Gd₂O₃+Y₂O₃) scope is 0.2-0.55, further preferred Gd₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) scope is 0.25-0.5, Still more preferably Gd₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) scope is 0.25-0.45, can at utmost it overcome because reducing or not making Use Ta₂O₅The ill effect that caused stability, glass declines, obtains the high-refractivity and low-dispersion with excellent stability, glass Glass, while glass not easy coloring.

Yb₂O₃And a kind of imparting height refraction, the component of low dispersion, when its introduction volume is more than 10%, glass resists Crystallization property can decline, therefore its content is defined to 0-10%, preferably 0-5%.

In glass of the present invention, Nb₂O₅When content is more than 0, there is fabulous effect to reducing liquidus temperature, it may have do not make Transmitance improves the effect of glass refraction, devitrification resistance and chemical durability, appropriate Nb in the case of being deteriorated₂O₅Introduce, also The devitrification resistance energy of glass can be effectively improved during accurate die pressing；If its content, more than 8%, glass dispersion carries Height, it is unable to reach the optical characteristics of glass of the present invention.Therefore, Nb₂O₅Content range be more than 0 but less than or equal to 8%, it is excellent It is 0.1-6% to select scope.Study and find through the present inventor, Nb in glass of the present invention₂O₅Content and Gd₂O₃The ratio Nb of content₂O₅/ Gd₂O₃For 0.01-0.45 when, the chemical durability and devitrification resistance of glass can be significantly improved, especially work as Nb₂O₅/Gd₂O₃For During 0.01-0.4, effect is especially apparent, more preferably 0.02-0.35, is still more preferably 0.05-0.25.

Ta₂O₅The viscosity of the refractive index of glass, devitrification resistance and molten glass can be improved, but its is expensive, it is unfavorable In the reduction of cost of material, therefore its content is defined to less than 8%, preferably less than 5%, more preferably less than 1%, further Preferably it is added without.

Ta is controlled in optical glass of the present invention₂O₅/Nb₂O₅Value be less than 1, in effectively regulation refractive index and while dispersion The devitrification resistance energy of glass can be improved, in addition, when containing easy coloring composition in glass, preferably Ta₂O₅/Nb₂O₅Value be less than 0.8, the tinctorial property of glass, further preferred Ta can be effectively improved₂O₅/Nb₂O₅Value be less than 0.5, still more preferably Ta₂O₅/Nb₂O₅Value be less than 0.3.

ZnO is added in body series glass, can be adjusted refractive index and the dispersion of glass, be improved the devitrification resistance energy of glass, The transition temperature of glass is reduced, lifts the stability of glass.ZnO can also reduce the high temperature viscosity of glass so that glass can be with Melting at a lower temperature, so as to lift the transmitance of glass.Especially when a small amount of containing not containing even in glass of the present invention When having tantalum oxide, by introducing more than 11% ZnO, the reduction of optical constant can be made up to a certain degree.But if ZnO is added Amount is excessive, and the devitrification resistance of glass be able to can decline, while high temperature viscosity is smaller, and difficulty is brought to shaping.In vitreum of the present invention In system, if ZnO content does not reach design requirement less than 11%, Tg temperature；If its content is higher than 30%, the anti-crystallization of glass Performance can decline, and high temperature viscosity does not reach design requirement.Therefore, ZnO content lower limit is 11%, and preferred lower limit is 15%；ZnO upper content limit is defined to 30%, preferred upper limit 25%.

For the present invention in order to obtain relatively low Tg temperature and stability is good, is easy to the glass of fusing, inventor passes through lot of experiments Research is found, as ZnO/ (B₂O₃+SiO₂) ratio range be 0.3-2, preferably ZnO/ (B₂O₃+SiO₂) ratio range be 0.5- 1.8, further preferred ZnO/ (B₂O₃+SiO₂) ratio range when being 0.5-1.45, the stability and Tg temperature of glass are up to most Good balance, obtain the preferable product of quality.

Meanwhile in order that glass in the case of with suitable Tg temperature, has excellent devitrification resistance energy, preferably controlled Nb processed₂O₅/ ZnO value is in the range of 0.01-0.5, more preferably 0.02-0.35, is still more preferably 0.03-0.25.

ZrO₂It is a kind of high refractive low dispersive oxide, the refractive index of glass can be lifted in glass and adjust color by adding Dissipate.Meanwhile proper amount of ZrO₂Add in glass, the devitrification resistance energy of glass can be lifted and into glass stability.In the present invention In, if its content is higher than 15%, glass can become to be difficult to melt, and smelting temperature can rise, and easily cause inside glass to press from both sides Debris and its transmitance decline.Therefore, its content is set greater than 0 but is less than or equal to 15%, preferably 1-10%, further Preferably 2-8%.

TiO₂It is a kind of high-refraction high-dispersion oxide, the refractive index and color of glass can be obviously improved by adding in glass Dissipate.The inventors discovered that TiO is added in right amount₂Into glass of the present invention, stability, glass, especially devitrification resistance can be increased Energy.If but excessive TiO₂Add 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 deteriorate.Therefore TiO₂Content be 0-8%, preferably 0-5%, more preferably 0-2%. Preferably make TiO in the present invention₂/(TiO₂+Nb₂O₅) value control in 0.01-0.8, can effectively adjust glass crystallization property and Chemical durability, more preferably TiO₂/(TiO₂+Nb₂O₅) it is 0.05-0.7, further preferred TiO₂/(TiO₂+Nb₂O₅) it is 0.1- 0.6。

WO₃Main function in glass is to maintain optical constant, improves devitrification of glass, but its too high levels, can make glass Glass transmitance reduces, degree of staining increase, and crystallization property degenerates.So WO₃Preferred content be 0-15%, more preferably content It is 0-10%, further preferred content is 0-7%.

WO₃、Nb₂O₅、ZrO₂、TiO₂It is favourable to the optical constant of maintenance glass, when it adds up to content (WO₃+Nb₂O₅+ZrO₂+ TiO₂) when being 1-30%, the devitrification resistance energy of glass, more preferably preferably 2-20%, 4-15% can be significantly improved；Especially Work as Nb₂O₅、ZrO₂、TiO₂Total amount (Nb₂O₅+ZrO₂+TiO₂) when being 1-25%, it can further optimize the chemical durability of glass With it is into glassy, preferably total amount is 2-20%, more preferably 4-15%.

WO₃And TiO₂Excessive introducing, can all make the transmitance of glass reduce, however the two and to the devitrification resistance of glass There can be preferable effect, be found by research of the inventor to the system optical glass, as (WO₃+Ta₂O₅+Nb₂O₅)/(ZrO₂ +TiO₂) control in the range of 0.1-5 when, not only can be very good to meet transmitance and the balance of crystallization property, and can enter The chemical stability of one-step optimization glass, further preferred (WO₃+Ta₂O₅+Nb₂O₅)/(ZrO₂+TiO₂) value be 0.1-3, more Further preferably (WO₃+Ta₂O₅+Nb₂O₅)/(ZrO₂+TiO₂) value be 0.1-1.Especially, the present inventor is to have glass Have excellent devitrification resistance can and high refractive low dispersive optical characteristics while, ensure that glass has good transmitance and low Cost advantage, found by lot of experiments, by controlling ZnO/ (WO₃+Ta₂O₅+Nb₂O₅+TiO₂) more than 1.8, preferably For 3-15, it is still more preferably 4-12, preceding aim can be reached.

It is a small amount of to introduce Al₂O₃It can improve and form the stability and chemical stability of glass, but when its content is more than 10%, show Show the tendency that glass melting is deteriorated, devitrification resistance reduces, therefore Al of the present invention₂O₃Content be 0-10%, preferably 0-5%, More preferably 0-1%, do not introduce further preferably.

Rn₂O is selected from Li₂O、Na₂O、K₂One or more in O, it can improve the meltbility of glass, and reduce glass The Tg temperature of glass.As Rn in glass₂When O content is limited to less than 10%, glass refraction can be made to be not easy to reduce, devitrification resistance is steady It is fixed, therefore, Rn₂O content is defined to 0-10%, preferably 0-5%, more preferably 0-2%.

Li₂O is added in glass ingredient, can effectively reduce the Tg temperature of glass.But low softening point optical glass leads to Often use platinum or platinum alloy vessel melting, during high melt, the Li in glass ingredient⁺Easily corrosion platinum or platinum alloy device Ware, cause to produce more platiniferous foreign matter in finished glass, cause the quality decline of glass.In addition in the present invention, more than 2% Li₂O can be such that the crystallization property of glass drastically declines, and therefore, its content is defined to 0-2%, preferably 0-1%.

Na₂O and K₂O is to reducing the effective any conditions of Tg, if its content is excessive, easily causing in devitrification temperature Rise and be difficult to vitrifying, therefore its content is defined to 0-10%, more preferably 0-5%, more preferably 0-1% respectively.

RO (one or more in RO MgO, CaO, SrO or BaO) can improve the meltbility of glass, adjust glass light Property, but when its content is more than 10%, the devitrification resistance of glass reduces, therefore in the present invention, RO contents are 0-10%, more preferably Scope is 0-5%, more preferably 0-1%, still more preferably not introduce.

P₂O₅It is the optional member for the devitrification resistance that can improve glass, especially by making P₂O₅Content for 10% with Under, the reduction of the chemical durability especially water resistance of glass can be suppressed.It is total accordingly, with respect to the glass of oxide conversion composition Quality, its content are defined to less than 10%, preferably less than 5%, more preferably less than 3%, not introduced further preferably.

Bi₂O₃It is that can improve glass refraction in right amount, reduces the optional member of glass transition temperature, when its content exceedes When 10%, glass devitrification resistance reduces, therefore its content is defined to less than 10%, preferably less than 5%, more preferably Less than 1%, do not introduce still more preferably.

GeO₂It is with the composition for improving glass refraction and increase devitrification resistance effect, is appointing for optical glass of the present invention Hank point, but its price is high, excessive introduce does not reach the purpose that the present invention reduces production cost, therefore its content is defined to Less than 8%, preferably less than 5%, are further defined to less than 2%, and further selection does not introduce.

If less than 10% Lu is introduced in the present invention₂O₃, can be acted synergistically with other terres rares components, so as to further The stability of glass is improved, but its is expensive, is introduced into glass and is then unfavorable for reducing production cost, therefore its content is defined to Less than 10%, preferably less than 5%, more preferably less than 3%, still more preferably not introduce.

As optional member of the present invention, by controlling Ga₂O₃Below 10%, the devitrification resistance of glass, and energy can be improved Enough increase the abrasion degree of glass, therefore its content is preferably less than 10%, more preferably less than 5%, still more preferably For less than 3%, do not introduce further preferably.

TeO₂It is to improve the refractive index of glass and reduce the optional member of the transition temperature of glass, when its content is excessive, Easily reacted with platinum crucible, be unfavorable for the service life of equipment.Therefore TeO₂Content is defined to less than 10%, preferably 5% with Under, do not introduce more preferably.

By adding Sb on a small quantity₂O₃、SnO₂、CeO₂Component can improve the clarifying effect of glass, but work as Sb₂O₃Content exceedes When 1%, glass has the tendency of Clarification Performance reduction, simultaneously because its strong oxidation promotes the platinum of fusion cast glass or platinum closes The corrosion of gold vessel ware and the deterioration of mould, therefore the preferred Sb of the present invention₂O₃Addition be 0-1%, more preferably 0- 0.5%, further preferably it is added without.SnO₂Fining agent can also be used as to add, but when its content is more than 1%, then glass It can colour, or when heating, softening glass and when carrying out die forming etc. and shaping again, Sn can turn into the starting point of nucleus generation, Produce the tendency of devitrification.Therefore the SnO of the present invention₂Content be preferably 0-1%, more preferably 0-0.5%, further preferably not Addition.CeO₂Effect and addition ratio and SnO₂Unanimously, its content is preferably 0-1%, more preferably 0-0.5%, further It is preferred that do not add.

F is low dispersion, reduces the effective component of glass transition temperature, but works as it and excessively contain sometimes, display glass folding The rate of penetrating significantly reduces, or glass melts the volatility increase of liquid, and glass reflects caused by texture, or volatilization can be produced when melting liquid shaping Rate changes the tendency of increase.F can use YF as raw material₃、LaF₃、GdF₃、ZrF₄、ZnF₂, alkali metal fluoride or alkaline earth gold Belong to fluoride to introduce.It is 0-10%, more preferably 0-5% that preferably F of the invention content, which accounts for optical glass total content, further excellent Elect as and do not introduce.

In order to preferably reach the purpose of the present invention, each component represents by weight percentage in glass, preferably SiO₂、B₂O₃、 La₂O₃、Gd₂O₃、Y₂O₃、TiO₂、Nb₂O₅、WO₃、ZrO₂Total content with ZnO is more than 95%, and is free of Ta₂O₅；More preferably SiO₂、B₂O₃、La₂O₃、Gd₂O₃、Y₂O₃、TiO₂、Nb₂O₅、WO₃、ZrO₂Total content with ZnO is more than 99%；Further preferably SiO₂、B₂O₃、La₂O₃、Gd₂O₃、Y₂O₃、TiO₂、Nb₂O₅、ZrO₂Total content with ZnO is more than 99%.

[on the composition that should not contain]

Do not damage the present invention glass performance in the range of, can add as needed it is above-mentioned do not referred to other into Point.But the transiting metal component such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo, even if contain on a small quantity independent or compoundly In the case of, glass is also subject to coloration, and the specific wavelength in visible region produces absorption, can so as to weaken the raising of the present invention The property of light transmission rate effect is seen, therefore it is desirable, especially for the optical glass that the transmitance of visible region wavelength requires, excellent Choosing does not include actually.

Pb, Th, Cd, Tl, Os, Be and Se cation, there is control to use as harmful chemical substance in recent years Tendency, not only in the manufacturing process of glass, until the measure in disposal after manufacturing procedure and commercialization to environmental protection It is required.Therefore, in the case where paying attention to the influence of environment, in addition to being inevitably mixed into, preferably actually not Contain them.Thus, optical glass becomes the material for not including pollution environment actually.Therefore, even if not taking special ring Measure in the countermeasure of border, optical glass of the invention also can be manufactured, processed and discarded.

Below, the characteristic of the optical glass of the present invention is illustrated.

[optical constant of optical glass]

The optical glass of the present invention is high-refractivity and low-dispersion glass, lens made of high-refractivity and low-dispersion glass it is more with Lens made of high index of refraction high-dispersion glass are combined, for chromatic aberration correction.The optical glass of the present invention is suitable to it from imparting From the point of view of the optical characteristics of purposes, the scope of glass refraction (nd) is 1.77-1.85, and preferable scope is 1.78- 1.84, preferred scope is 1.785-1.84；Abbe number (the ν of glass of the present invention_d) scope be 40-48, preferred scope is 41-47。

[transition temperature of optical glass]

Optical glass gradually can become mouldable state in a certain temperature range by solid-state.Transition temperature refers to glass specimen from room Temperature is warming up to temperature of hanging down of speeding, the temperature corresponding to intersection point that its low-temperature region and high-temperature area straight line portion extended line intersect.

The transition temperature (Tg) of glass of the present invention preferably less than 620 DEG C, more preferably less than 615 DEG C, enters below 630 DEG C One step is preferably less than 610 DEG C.

[coloring of optical glass]

The shortwave transmitted spectrum characteristic degree of staining (λ of glass of the present invention₈₀/λ₅) represent.λ₈₀Refer to that glass transmittance reaches Corresponding wavelength, λ when 80%₅Refer to that glass transmittance reaches corresponding wavelength when 5%.Wherein, λ₈₀Measure be that use has The glass that the thickness of two parallel to each other and optical polish relative planes is 10 ± 0.1nm, is determined from 280nm to 700nm Spectral transmission in wavelength domain simultaneously shows the wavelength of transmissivity 80%.So-called spectral transmission or transmissivity are to glass Above-mentioned surface vertically incident intensity I_inLight, project intensity I through glass and from plane_outLight in the case of lead to Cross I_out/I_inThe amount of expression, and also contains the transmissivity of the surface reflection loss on the above-mentioned surface of glass.The folding of glass It is higher to penetrate rate, surface reflection loss is bigger.Therefore, in glass of high refractive index, λ₈₀The small coloring for meaning glass itself of value Seldom.

The optical glass λ of the present invention₈₀Less than or equal to 410nm, preferably λ₈₀Scope be less than or equal to 405nm, it is more excellent Select λ₈₀Scope be less than or equal to 400nm, further preferred λ₈₀Scope be less than or equal to 395nm, it is further excellent The λ of choosing₈₀Scope be less than or equal to 390nm.λ₅Less than or equal to 350nm, preferably λ₅Scope be less than or equal to 345nm, more preferably λ₅Scope be less than or equal to 340nm, further preferred λ₅Scope be less than or equal to 335nm.

[density of optical glass]

The density of optical glass is the quality of unit volume when temperature is 20 DEG C, and unit is with g/cm³Represent.

The density (ρ) of glass of the present invention is in 5.00g/cm³Hereinafter, preferably 4.90g/cm³Below.

[crystallization ceiling temperature]

The crystallization property of glass is determined using temperature gradient furnace method, glass is made to 180*10*10mm sample, side polishes, It is put into the stove inside holding with thermograde to take out after 4 hours, crystal occur in sight glass crystallization situation, glass under the microscope Corresponding maximum temperature is the crystallization ceiling temperature of glass.The crystallization ceiling temperature of glass is lower, then glass is steady in high temperature Qualitative stronger, the processing performance of production is better.

The recrystallization temperature of glass of the present invention is below 1160 DEG C, preferably less than 1155 DEG C, more preferably 1150 DEG C Hereinafter, it is still more preferably 1140 DEG C below.

IIth, gas preform and optical element

Below, the optical precast product and optical element of the present invention is described.

The gas preform of the present invention is formed with optical element by the optical glass of the invention described above.The glass of the present invention Prefabricated component has high-refractivity and low-dispersion characteristic；The optical element of the present invention has high-refractivity and low-dispersion characteristic, can be with low Cost provides the optical elements such as the costly various lens of optics, prism.

As the example of lens, can enumerate lens face for sphere or aspherical recessed meniscus shaped lens, male bend moon-shaped lens, The various lens such as biconvex lens, biconcave lens, planoconvex spotlight, plano-concave lens.

This lens by with high index of refraction high-dispersion glass made of lens combination, recoverable aberration, be suitable as color The lens of poor correction.In addition, the densification for optics system is also effective lens.

For prism, because refractive index is high, therefore by combining in camera optical system, by bending light path, Towards required direction, you can realize compact, wide-angle optics system.

Embodiment

The present invention is explained using following examples, but the present invention should not be limited to these embodiments.

The melting and forming method for producing optical glass can be using well known to a person skilled in the art technology.Glass is former Material (carbonate, nitrate, sulfate, hydroxide, oxide, boric acid etc.) is weighed with merging according to the proportioning of glass oxide After well mixed, put into smelting apparatus (such as platinum crucible), then taken at 1150~1400 DEG C appropriate stirring, clarification, After homogenizing, less than 1250 DEG C are cooled to, cast or leakage note are in mould, the post-processing such as last annealed, processing, or It is molded by precise compression molding technology direct pressing.

[optical glass embodiment]

In addition, defining the characteristic of each glass of the present invention by method as shown below, and measurement result is represented in table 1 In~table 6, wherein, represent SiO with A1₂+B₂O₃Value, A2 represent La₂O₃+Gd₂O₃+Y₂O₃Value, A3 represent WO₃+Nb₂O₅+ ZrO₂+TiO₂Value, K1 represent Ta₂O₅/Nb₂O₅Value, K2 represent SiO₂/(SiO₂+B₂O₃), K3 represents Nb₂O₅/Gd₂O₃Value, K4 represents Gd₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) value, K5 represent (WO₃+Ta₂O₅+Nb₂O₅)/(ZrO₂+TiO₂) value, K6 represent ZnO/(SiO₂+B₂O₃) value, K7 represent Nb₂O₅/ ZnO value, K8 represent TiO₂/(TiO₂+Nb₂O₅) value, K9 represent ZnO/ (WO₃+Ta₂O₅+Nb₂O₅+TiO₂)。

(1) refractive index nd and Abbe number ν d

Refractive index is tested with Abbe number according to method as defined in GB/T7962.1-2010.

(2) glass coloration degree (λ₈₀/λ₅)

Use the glass sample that the thickness with two optical polish planes relative to each other is 10 ± 0.1mm, measure point Light transmission, it is calculated according to its result.

(3) glass transformation temperature (Tg)

Method measures as defined in GB/T7962.16-2010.

(4) density (ρ) of glass

Method measures as defined in GB/T7962.20-2010.

(5) crystallization ceiling temperature

The crystallization property of glass is determined using temperature gradient furnace method, glass is made to 180*10*10mm sample, side polishes, It is put into the stove inside holding with thermograde to take out after 4 hours, crystal occur in sight glass crystallization situation, glass under the microscope Corresponding maximum temperature is the crystallization ceiling temperature of glass.

(6) the crystallization situation in glass production shaping

Glass flows out to and block is shaped in mould after melting, clarification, homogenizing by platinum or platinum alloy discharge nozzle Material or moulding mixture, occur crystal with surface, inside glass or surface inside sight glass after glass cooling and show devitrification of glass performance Deficiency.Inside glass and surface do not have crystallization crystal to occur being represented with " A ", and internal or surface has crystallization crystal to occur using " O " table Show.

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

[gas preform embodiment]

Optical glass obtained by embodiment 1-10 in table 1 is cut into predefined size, then is equably coated with the surface Releasing agent, be then heated, soften, be press-formed, make recessed meniscus shaped lens, male bend moon-shaped lens, biconvex lens, The various lens such as biconcave lens, planoconvex spotlight, plano-concave lens, the prefabricated component of prism.

[optical element embodiment]

These prefabricated components obtained by above-mentioned gas preform embodiment are annealed, are reducing the same of the deformation of inside glass When be finely adjusted so that the optical characteristics such as refractive index reaches 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, planoconvex spotlight, plano-concave lens, prism.Antireflection can be also coated with the surface of gained optical element Film.

The present invention is the optical glass of inexpensive and excellent chemical stability high refractive low dispersive, and refractive index is 1.77-1.85, Abbe number 40-48, and the optical element that the glass is formed, disclosure satisfy that Modern New photovoltaic Need.

Claims

1. optical glass, it is characterised in that its refractive index is 1.77-1.85, Abbe number 40-48, and it forms percentage by weight Than representing, contain：SiO₂+B₂O₃：15-40%；La₂O₃+Gd₂O₃+Y₂O₃：35-70%；WO₃+Nb₂O₅+ZrO₂+TiO₂：1-30%； ZnO：11-30%；Nb₂O₅/Gd₂O₃For 0.01-0.45.

2. optical glass as claimed in claim 1, it is characterised in that its composition represents by weight percentage, also contains： Al₂O₃：0-10%；Ta₂O₅：0-8%；Rn₂O：0-10%, wherein Rn₂O is Li₂O、Na₂O、K₂One or more in O；RO：0- 10%, wherein RO are the one or more in MgO, CaO, SrO or BaO.

3. the optical glass as described in any claim of claim 1 or 2, it is characterised in that：SiO₂+B₂O₃：18-38%； And/or La₂O₃+Gd₂O₃+Y₂O₃：35-65%；And/or WO₃+Nb₂O₅+ZrO₂+TiO₂：2-20%；Rn₂O：0-5%, wherein Rn₂O For Li₂O、Na₂O、K₂One or more in O；RO：0-5%, wherein RO are the one or more in MgO, CaO, SrO or BaO.

4. the optical glass as described in any claim of claim 1 or 2, it is characterised in that：SiO₂+B₂O₃：20-35%； And/or La₂O₃+Gd₂O₃+Y₂O₃：38-60%；And/or WO₃+Nb₂O₅+ZrO₂+TiO₂：4-15%；Rn₂O：0-2%, wherein Rn₂O For Li₂O、Na₂O、K₂One or more in O；RO：0-1%, wherein RO are the one or more in MgO, CaO, SrO or BaO.

5. the optical glass as described in any claim of claim 1 or 2, it is characterised in that：The content of each component meet with One or more in lower 9 kinds of conditions：

1)Ta₂O₅/Nb₂O₅：Less than 1；

2)ZnO/(SiO₂+B₂O₃) it is 0.3-2；

3)Gd₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) it is 0.2-0.55；

4)SiO₂/(SiO₂+B₂O₃) it is 0.2-0.6；

5)Nb₂O₅/Gd₂O₃For 0.01-0.4；

6)(WO₃+Ta₂O₅+Nb₂O₅)/(ZrO₂+TiO₂) it is 0.1-5；

7)Nb₂O₅/ ZnO is 0.01-0.5；

8)TiO₂/(TiO₂+Nb₂O₅) it is 0.01-0.8；

9)ZnO/(WO₃+Ta₂O₅+Nb₂O₅+TiO₂) it is more than 1.8.

6. the optical glass as described in any claim of claim 1 or 2, it is characterised in that wherein：Nb₂O₅+ZrO₂+TiO₂： 1-25%.

7. the optical glass as described in any claim of claim 1 or 2, it is characterised in that wherein：Nb₂O₅：It is more than 0 but small In or equal to 8%；ZrO₂：More than 0 but less than or equal to 15%；TiO₂：0-8%；WO₃：0-15%.

8. the optical glass as described in any claim of claim 1 or 2, it is characterised in that wherein：La₂O₃：20-40%； Gd₂O₃：11-30%；Y₂O₃：0-15%.

9. the optical glass as described in any claim of claim 1 or 2, it is characterised in that wherein：SiO₂：4-20%； B₂O₃：8-24%；Li₂O：0-2%；Na₂O：0-10%；K₂O：0-10%.

10. the optical glass as described in any claim of claim 1 or 2, it is characterised in that wherein：SiO₂：5-18%； And/or B₂O₃：10-23%；And/or La₂O₃：20-35%；And/or Gd₂O₃：11-25%；And/or Y₂O₃：0-10%；And/or WO₃：0-10%；And/or Ta₂O₅：0-5%；And/or Nb₂O₅：0.1-6%；And/or ZrO₂：1-10%；And/or ZnO：15- 30%；And/or TiO₂：0-5；And/or Al₂O₃：0-5%；And/or Li₂O：0-1%；And/or Na₂O：0-5%；And/or K₂O：0- 5%；And/or Sb₂O₃：0-0.5%；And/or RO：0-5%, wherein, the one or more in RO MgO, CaO, SrO or BaO.

11. the optical glass as described in any claim of claim 1 or 2, it is characterised in that wherein：SiO₂：6-15%； And/or B₂O₃：12-20%；And/or La₂O₃：22-32%；And/or Gd₂O₃：12-22%；And/or Y₂O₃：0-8%；And/or WO₃：0-7%；And/or ZrO₂：2-8%；And/or ZnO：15-25%；And/or TiO₂：0-2%.

12. the optical glass as described in any claim of claim 1 or 2, it is characterised in that wherein：Ta₂O₅/Nb₂O₅：It is small In 0.8；And/or ZnO/ (SiO₂+B₂O₃) it is 0.5-1.8；And/or Gd₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) it is 0.25-0.5；And/or SiO₂/(SiO₂+B₂O₃) it is 0.23-0.5；And/or Nb₂O₅/Gd₂O₃For 0.02-0.35；And/or (WO₃+Ta₂O₅+Nb₂O₅)/ (ZrO₂+TiO₂) it is 0.1-3；And/or Nb₂O₅/ ZnO is 0.02-0.35；And/or TiO₂/(TiO₂+Nb₂O₅) it is 0.05-0.7； And/or ZnO/ (WO₃+Ta₂O₅+Nb₂O₅+TiO₂) it is 3-15.

13. the optical glass as described in any claim of claim 1 or 2, it is characterised in that wherein：Ta₂O₅/Nb₂O₅：It is small In 0.5；ZnO/(SiO₂+B₂O₃) it is 0.5-1.45；And/or Gd₂O₃/(La₂O₃+Gd₂O₃+Y₂O₃) it is 0.25-0.45；And/or SiO₂/(SiO₂+B₂O₃) it is 0.25-0.45；And/or Nb₂O₅/Gd₂O₃For 0.05-0.25；And/or (WO₃+Ta₂O₅+Nb₂O₅)/ (ZrO₂+TiO₂) it is 0.1-1；And/or Nb₂O₅/ ZnO is 0.03-0.25；And/or TiO₂/(TiO₂+Nb₂O₅) it is 0.1-0.6；With/ Or ZnO/ (WO₃+Ta₂O₅+Nb₂O₅+TiO₂) it is 4-12.

14. the optical glass as described in any claim of claim 1 or 2, it is characterised in that wherein：Nb₂O₅+ZrO₂+ TiO₂：2-20%；La₂O₃+Gd₂O₃+Y₂O₃：40-55%.

15. the optical glass as described in any claim of claim 1 or 2, it is characterised in that wherein：Nb₂O₅+ZrO₂+ TiO₂：4-15%.

16. the optical glass as described in any claim of claim 1 or 2, it is characterised in that wherein：SiO₂、B₂O₃、 La₂O₃、Gd₂O₃、Y₂O₃、TiO₂、Nb₂O₅、WO₃、ZrO₂Total content with ZnO is more than 95%, and is free of Ta₂O₅。

17. the optical glass as described in any claim of claim 1 or 2, it is characterised in that wherein：SiO₂、B₂O₃、 La₂O₃、Gd₂O₃、Y₂O₃、TiO₂、Nb₂O₅、ZrO₂Total content with ZnO is more than 99%.

18. the optical glass as described in any claim of claim 1 or 2, it is characterised in that it is formed by weight percentage Represent, contain：

Yb₂O₃：0-10%；

P₂O₅：0-10%；

Bi₂O₃：0-10%；

TeO₂：0-10%；

Ga₂O₃:0-10%；

Lu₂O₃:0-10%；

GeO₂：0-8%；

CeO₂：0-1%；

SnO₂：0-1%；

Sb₂O₃：0-1%；

F：0-10%.

19. the optical glass as described in any claim of claim 1 or 2, it is characterised in that it is formed by weight percentage Represent, contain：

Yb₂O₃：0-5%；

P₂O₅：0-5%；

Bi₂O₃：0-5%；

TeO₂：0-5%；

Ga₂O₃:0-5%；

Lu₂O₃:0-5%；

GeO₂：0-5%；

CeO₂：0-0.5%；

SnO₂：0-0.5%；

Sb₂O₃：0-1%；

F：0-5%.

20. the optical glass as described in claim 1-19 any claims, it is characterised in that the transmittance of glass reaches Corresponding wavelength X when 80%₈₀For below 410nm, transmittance reaches corresponding wavelength X when 5%₅For below 350nm；The crystallization upper limit Temperature is below 1160 DEG C；Glass transformation temperature is less than 630 DEG C；The density of glass is 5.00g/cm³Below.

21. the optical glass as described in claim 1-19 any claims, it is characterised in that the transmittance of glass reaches Corresponding wavelength X when 80%₈₀For below 400nm, transmittance reaches corresponding wavelength X when 5%₅For below 340nm；The crystallization upper limit Temperature is below 1150 DEG C；Glass transformation temperature is less than 620 DEG C；The density of glass is 4.90g/cm³Below.

22. gas preform, it is made of the optical glass described in claim 1-21 any claims.

23. optical element, it is made of the optical glass described in claim 1-21 any claims.