CN109205616A - Optical glass, gas preform, optical element and optical instrument - Google Patents

Optical glass, gas preform, optical element and optical instrument Download PDF

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Publication number
CN109205616A
CN109205616A CN201811391994.9A CN201811391994A CN109205616A CN 109205616 A CN109205616 A CN 109205616A CN 201811391994 A CN201811391994 A CN 201811391994A CN 109205616 A CN109205616 A CN 109205616A
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glass
bao
sro
optical glass
cao
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CN109205616B (en
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毛露路
匡波
吴德林
周佺佺
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CDGM Glass Co Ltd
Chengdu Guangming Optoelectronics Co Ltd
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Chengdu Guangming Optoelectronics Co Ltd
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Priority to CN201811391994.9A priority Critical patent/CN109205616B/en
Publication of CN109205616A publication Critical patent/CN109205616A/en
Priority to JP2021528467A priority patent/JP7250130B2/en
Priority to PCT/CN2019/111159 priority patent/WO2020103607A1/en
Priority to TW108139276A priority patent/TWI798501B/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/004—Refining agents
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)

Abstract

The present invention provides a kind of medium refractive index and the low optical glass of thermal refractive index coefficient, and composition includes SiO2、B2O3、La2O3, RO and Rn2The optical glass of O, wherein RO be one of MgO, CaO, SrO and BaO or more than one, Rn2O is Li2O、K2O and Na2One of O or more than one, the refractive index of the optical glass is 1.65~1.73, and Abbe number is 47~55, while having lower thermal refractive index coefficient, excellent devitrification resistance energy and chemical stability.

Description

Optical glass, gas preform, optical element and optical instrument
Technical field
The present invention relates to a kind of optical glass, be 1.65~1.73 more particularly, to a kind of refractive index, Abbe number be 47~ 55 optical glass containing lanthanum, and the gas preform made of the optical glass, optical element and optical instrument.
Background technique
In the prior art, the glass that refractive index is 1.65~1.73, Abbe number is 47~55 belongs to medium refractive index glass Glass is widely applied in all kinds of camera lenses.In recent years, on-vehicle lens equipment has obtained the applications such as vigorous growth, and general photography It compares, the quality of on-vehicle lens is closely bound up with safety, therefore on-vehicle lens more emphasize the reliability of equipment, especially exposed Outside car body, need to bear harsh environments, such as backup camera, forward sight camera, rearview mirror second camera head.
It is that structure is simple as far as possible that design, which meets the principle of harsh environments on-vehicle lens, and structure is more complicated, reliably Property is poorer.Therefore, in order to meet the design of the on-vehicle lens long-life (up to 10 years or more) for being suitable for harsh environments It is required that generally being designed using tight shot in optical design, number of lenses is fewer than zoom lens, while not having zoom drive Structure, therefore reliability is improved significantly compared with zoom lens.
But although tight shot reliability is very good, apply on vehicle-mounted, fatal weakness is to correct camera lens Temperature drift be very difficult.The temperature drift of camera lens refers to when acute variation occurs for temperature, such as desert area Day and night temperature reaches 60 DEG C, and automobile drives under the very big scene of the temperature difference such as frigid zone from the torrid zone, and the focal length of camera lens can become Change, so as to cause image blur.For automobile, be safely it is primary, therefore, vehicle-mounted camera need temperature sharply Under conditions of variation, it is able to maintain and is clearly imaged.
For optical design, it can usually be solved using more different types of lens combinations and zoom system, pancreatic system Temperature drift problems.But the requirement due to onboard system to reliability, it needs in number of lenses seldom (even 3) Temperature drift problems are solved in fixed-focus imaging system, this just needs to develop the optical glass with special temperature refraction rate coefficient, This is also the new issue researching and proposing to optical design and optical material of development in epoch.
The optical glass that the refractive index of currently available technology is 47~55 in 1.65~1.73, Abbe number, 20~40 Within the scope of DEG C, thermal refractive index coefficient value, i.e. d line dn/dt relative (10-6/ DEG C) substantially 1.0~3.0 (10-6/℃) Left and right (see the table below 1).If can develop thermal refractive index coefficient lower than 0, even lower than -1.0 and be in the above photosensitiveness lanthanum Crown glass can effectively solve above-mentioned temperature drift problems in the design.
Table 1: the thermal refractive index coefficient that fractional index is 1.65~1.73, Abbe number is the glass in 47~55 ranges
Serial number nd νd Within the scope of 20~40 DEG C, d line dn/dt relative (10-6/℃)
Example 1 1.72916 54.70 2.8
Example 2 1.69350 50.80 2.3
Example 3 1.66461 54.61 1.9
But if desired the lanthanum crown glass of above-mentioned refractive index and Abbe number reaches the thermal refractive index coefficient lower than 0, in group Set up separately need to be different from meter it is conventional, it will usually to bringing glass devitrification resistance poor in production, striped bubble, which is not easy to eliminate, etc. is asked Topic.
If the anti-crystallization ability of glass is poor, it will increase the production difficulty of glass raw material first, yields caused to decline, sternly It even cannot normally be produced when weight；It is followed by easy to produce crystal precipitation during secondary press, causes yields to decline, very To not can be carried out secondary press.For applying in the glass material of automotive field, if the production yields of glass is low, and Using secondary press but the method production being cold worked cannot be used, cost increase, which will will lead to, to be difficult to receive.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of medium refractive index and the low optics of thermal refractive index coefficient Glass.
The technical proposal for solving the technical problem of the invention is:
(1) optical glass, composition include SiO2、B2O3、La2O3, RO and Rn2O, wherein R0 is MgO, CaO, SrO and BaO One of or more than one, Rn20 is Li2O、K2O and Na2One of O or more than one, the refractive index of glass is 1.65~ 1.73, Abbe number is 47~55, and thermal refractive index coefficient is≤0.
(2) optical glass according to (1), composition in terms of weight percentage, contain: SiO2: 4~20%, B2O3: 10~30%, La2O3: 10~35%, BaO:10~40%, SrO:0~15%, CaO:0~10%, MgO:0~5%, Li2O:0~5%, K2O:0~6%, Na2O:0~8%, Gd2O3: 0~8%, Y2O3: 0~5%, ZrO2: 0~3%, Al2O3: 0 ~3%, TiO2: 0~3%, Nb2O5: 0~5%, WO3: 0~2%, ZnO:0~5%, clarifying agent: 0~2%.
(3) optical glass, composition in terms of weight percentage, contain: SiO2: 4~20%, B2O3: 10~30%, La2O3: 10~35%, BaO:10~40%, SrO:0~15%.
(4) optical glass according to (3), also contains: CaO:0~10%, MgO:0~5%, Li2O:0~5%, K2O:0~6%, Na2O:0~8%, Gd2O3: 0~8%, Y2O3: 0~5%, ZrO2: 0~3%, Al2O3: 0~3%, TiO2: 0 ~3%, Nb2O5: 0~5%, WO3: 0~2%, ZnO:0~5%, clarifying agent: 0~2%.
(5) optical glass forms in terms of weight percentage by SiO2: 4~20%, B2O3: 10~30%, La2O3: 10 ~35%, BaO:10~40%, SrO:0~15%, CaO:0~10%, MgO:0~5%, Rn20:0~8%, Gd2O3: 0~ 8%, Y2O3: 0~5%, ZrO2: 0~3%, Al2O3: 0~3%, TiO2: 0~3%, Nb2O5: 0~5%, WO3: 0~2%, ZnO:0~5% is formed, wherein Rn20 is Li2O、K2O、Na2One of O or more than one.
(6) according to any optical glass in (1)~(5), SiO2/B2O3It is 0.4~1.3, preferably 0.45~1.2, More preferably 0.5~1.1；And/or BaO/La2O3It is 0.6~2, preferably 0.65~1.9, more preferably 0.7~1.8.
(7) according to any optical glass in (1)~(6), CaO/ (BaO+SrO) is 0~0.5, preferably 0.01~ 0.4, more preferably 0.02~0.3；And/or ZnO/ (CaO+SrO+BaO) be 0~0.3, preferably 0~0.2, more preferably 0~ 0.15；And/or (CaO+SrO+BaO)/(La2O3+Gd2O3+Y2O3) it is 0.7~2.5, preferably 0.8~2.3, more preferably 0.9 ~2.1；And/or (CaO+SrO+BaO)/(Al2O3+ZrO2+TiO2) it is greater than 8, preferably greater than 10, more preferably greater than 12；And/or SrO content >=CaO content, preferably BaO content >=SrO content >=CaO content.
(8) according to any optical glass in (1)~(7), Li2O+Na2O+K2O is 0~8%, preferably 0~6%, More preferably 0~5%；And/or Li2O/(K2O+Na2It O) is 0~0.5, preferably 0~0.4, more preferably 0~0.3；And/or Na2O/K2O is 0.2~5.0, preferably 0.3~4.0, more preferably 0.4~3.0；And/or TiO2/Nb2O5For 1 hereinafter, it is preferred that For 0.8 hereinafter, more preferably 0.5 or less.
(9) according to any optical glass in (1)~(8), composition in terms of weight percentage, contains: SiO2: 6 ~18%, and/or B2O3: 12~25%, and/or La2O3: 12~30%, and/or BaO:12~35%, and/or SrO:0.5~ 15%, and/or CaO:0~8%, and/or Gd2O3: 1~6%, and/or Y2O3: 0~3%, and/or ZrO2: 0.1~3% and/ Or Al2O3: 0~2%, and/or TiO2: 0~2%, and/or Nb2O5: 0.1~5%, and/or WO3: 0~1%, and/or ZnO:0 ~3%, and/or MgO:0~3%, and/or Li2O:0~3%, and/or K2O:0.3~4%, and/or Na2O:0.5~6%.
(10) according to any optical glass in (1)~(9), composition in terms of weight percentage, contains: SiO2: 8 ~16%, and/or B2O3: 15~22%, and/or La2O3: 15~28%, and/or BaO:15~32%, and/or SrO:1~ 12%, and/or CaO:0~6%, and/or Gd2O3: 1~4%, and/or Y2O3: 1~3%, and/or ZrO2: 0.1~2% and/ Or Al2O3: 0.1~1%, and/or TiO2: 0~1%, and/or Nb2O5: 0.5~4%, and/or K2O:0.5~3%, and/or Na2O:1~3%.
(11) according to any optical glass in (1)~(10), composition in terms of weight percentage, contains: ZrO2: 0.1~1%, and/or Nb2O5: 1~3%, and/or SrO:1.5~10%.
(12) according to any optical glass in (1)~(11), the refractive index of glass is 1.65~1.73, preferably 1.67~1.72；Abbe number is 47~55, preferably 48~52.
(13) according to any optical glass in (1)~(12), the thermal refractive index coefficient of glass is≤0, preferably ≤ -0.5, more preferably≤- 1.0, further preferably≤- 2.0.
(14) according to any optical glass in (1)~(13), the water-resistant stability of glass be 4 classes and its more than, it is excellent Be selected as 3 classes and its more than, more preferably 2 classes and its more than；And/or bubble degree is A grades or more, preferably A0Grade or more, it is more excellent It is selected as A00Grade；And/or striped is C grades or more, preferably B grades or more, more preferably A grades；And/or resistance to sunshine stability is 400nm Transmitance decline is no more than 10%, preferably more than 8% at wavelength, is further preferably no more than 5%.
(15) gas preform is made of any optical glass in (1)~(14).
(16) optical element, using gas preform system described in (1)~(14) any optical glass or (15) At.
(17) optical instrument is made of optical element described in (1)~(14) any optical glass or (16).
(18) application of the optical element described in any optical glass or (16) of (1)~(14) in vehicle-mounted.
The beneficial effects of the present invention are: being designed by reasonable component, so that optical glass of the present invention has medium refractive Rate and low thermal refractive index coefficient, batch production technique performance are good.
Specific embodiment
In the following, being illustrated to the compositing range of each ingredient of optical glass of the present invention.In the present specification, if do not had Specified otherwise, the content of each component is all using the weight percent of the glass substance total amount relative to the composition for being converted into oxide Than indicating.Herein, described " composition for being converted into oxide " refers to, the raw material as optical glass constituent of the invention And in the case where decomposing when the melting such as oxide, complex salt and hydroxide used and be changed into oxide, by the oxide Substance total amount as 100%.
Unless in particular situations it is further noted that numberical range listed herein includes upper and lower bound value, " more than " " following " includes endpoint value, all integers and score in the range, and is not limited to listed specific when limited range Value.Term as used herein " about " assignment side, parameter and other quantity and feature be not and need not to be accurate, if any It needs, can be approximate and/or bigger or lower, this reflection tolerance, conversion factor and measurement error etc..Herein referred "and/or" It is inclusive, such as " A and/or B ", refers to only A, perhaps only B or has A and B simultaneously.
Optical glass of the present invention is mainly by SiO2、B2O3、La2O3, RO (one of R0 MgO, CaO, SrO, BaO or one Kind or more, it is the same below), Rn2O(Rn20 is Li2O、K2O、Na2One of O or more than one, it is the same below) composition, by reasonable Component proportion, form the optical glass that refractive index is 1.65~1.73, Abbe number is 47~55, and it is in 20~40 DEG C of temperature In range, thermal refractive index coefficient (d line dn/dt relative (10-6/ DEG C)) low, devitrification resistance can be excellent, is used for a long time saturating The rate of mistake will not be generated and is decreased obviously, and be very suitable for on-vehicle lens use.
SiO2And B2O3It is the Network former for constituting glass of the present invention, is the basis to form glass, content and glass It is closely bound up at key indexes such as glass stability, devitrification resistance energy, refractive index and Abbe numbers.Wherein, if SiO2Content is more than 20%, glass can become difficult to melt, while can decline at glass stability, and devitrification resistance can sharply decline, the refractive index of glass Design requirement is not achieved with Abbe number；If SiO2Content be lower than 4%, the chemical stability of glass, especially water-fast effect is steady Qualitative to decline, the devitrification resistance of glass can decline.Therefore, SiO2Content be limited to 4~20%, preferably 6~18%, More preferably 8~16%.In some embodiments, can include about 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20% SiO2。
B2O3If content more than 30%, the chemical stability of glass can decline, and Abbe number can be higher than expected design；B2O3 If content be lower than 10%, the devitrification resistance of glass can rapid decrease, and expected design is not achieved in the Abbe number of glass.Cause This, B2O3Content be limited to 10~30%, preferably 12~25%, more preferably 15~22%.In some embodiments, Can include about 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30% B2O3。
SiO2And B2O3Relative amount can determine B to a certain extent2O3Configuration state in glass, and B2O3Knot Structure state can thermal refractive index coefficient to glass and chemical stability generate large effect, work as SiO2With B2O3Ratio SiO2/B2O3When greater than 1.3, the thermal refractive index coefficient of glass can be increased quickly, and design requirement is not achieved；If SiO2/B2O3It is small When 0.4, chemical durability of glass, especially water resistance meeting rapid decrease are not able to satisfy the requirement used in mal-condition. Therefore, in the present invention, SiO2/B2O3Value be preferably limited to 0.4~1.3.In addition, in some embodiments, if SiO2/B2O3 Value less than 0.45, high temperature viscosity is minimum at the time of molding for glass, be easy inside glass generate C grades of stripeds below, cause glass Glass cannot be applied in more demanding imaging system, if SiO2/B2O3Value be higher than 1.2, the bubble of glass is difficult to eliminate.Cause This in some embodiments, SiO2/B2O3Value be more preferably 0.45~1.2, further preferably 0.5~1.1.Some In embodiment, SiO2/B2O3Value can for 0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85,0.9, 0.95、1.0、1.05、1.1、1.15、1.2、1.25、1.3。
La2O3It is the important composition ingredient of glass of the present invention, being added in glass can be made with the refractive index of fast lifting glass The performance of glass realization high-refractivity and low-dispersion.But if its content is more than 35%, the devitrification resistance of glass can sharply under Drop, more seriously, inventor study discovery La2O3There is strong concentration effect, it, can fast lifting when content is more than 35% The target of the thermal refractive index coefficient of glass, this thermal refractive index coefficient that reduce glass with the present invention is runed counter to；If its content Lower than 10%, design requirement, while the chemical stability of glass, especially water resistance meeting is not achieved in the refractive index of glass and dispersion It reduces.Therefore, La2O3Content be limited to 10~35%, preferably 12~30%, more preferably 15~28%.In some implementations In mode, can include about 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35% La2O3。
In order in La2O3Glass can also maintain preferable devitrification resistance energy in the case that comparision contents are high, and inventor studies hair It is existing, add a certain amount of Gd2O3、Y2O3、ZrO2、TiO2、Al2O3Etc. the devitrification resistance energy that can promote glass.
Specifically, Gd2O3Effect and La for refractive index and dispersion2O3It is similar, if but content be higher than 8%, the folding of glass Rate temperature coefficient meeting rapid increase, cost meeting rapid increase are penetrated, the devitrification resistance of glass can decline instead, therefore, content It is limited to 0~8%, preferably 1~6%, more preferably 1~4%.In some embodiments, it can include about 0%, be greater than 0%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% Gd2O3。
A small amount of Y2O3It is added in glass and substitutes La2O3The refractive index and dispersion that not will lead to glass have larger change, but If its content is more than 5%, the thermal refractive index coefficient meeting rapid increase of glass, the devitrification resistance of glass can decline.Therefore, Content is limited to 0~5%, preferably 0~3%, further preferably 1~3%.In some embodiments, it can include about 0%, the Y greater than 0%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%2O3。
ZrO2Optional components in the present invention, be added in glass on a small quantity the devitrification resistance energy that can promote glass and It is obviously improved the chemical stability of glass, while a small amount of ZrO is added2Glass metal can be significantly reduced in production process to fire proofed wood On the one hand the erosion of material can promote converter life, reduce the cost and trash discharge of furnace body maintenance, on the other hand can be significant Inhibit refractory material in impurity enter glass, promoted glass transmitance and anti-crystallization stability.But ZrO2In this system It is harmful to the thermal refractive index coefficient for reducing glass in glass, if its content is more than 3%, the thermal refractive index coefficient of glass Can fast lifting, design requirement is not achieved, while glass becomes to be very difficult to melt, devitrification resistance can rapid decrease, therefore, ZrO in the present invention2Content is limited to 3% or less.If ZrO2Content be lower than 0.1%, on glass is obvious to the erosion of refractory material It rises.Therefore, ZrO in the present invention2Content is preferably 0.1~3%, and more preferably 0.1~2%, further preferably 0.1~1%. In some embodiments, can include about 0%, be greater than 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3% ZrO2。
A small amount of Al2O3It is added in glass the devitrification resistance energy that can promote glass, while glass metal corruption can also be reduced Lose the ability of crucible material.But if its additive amount is higher than 3%, and the thermal refractive index coefficient of glass can rise, while glass melts Changing performance can decline, and refractive index also can rapid decrease.Therefore, content be limited to 3% hereinafter, preferably 2% hereinafter, more preferably It is 0.1~1%.In some embodiments, can include about 0%, be greater than 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3% Al2O3。
A small amount of TiO2It is added in glass, the resistance to sunshine stability of glass can be promoted, it is long especially for on-vehicle lens Phase is exposed to especially important in the intensive ultraviolets environment such as plateau.In addition, a small amount of TiO2The devitrification resistance energy of glass can be promoted.But TiO2For this system glass, the reduction of refractive index temperature coefficient is harmful.It is studied by inventor's a large number of experiments It was found that design requirement is not achieved in the thermal refractive index coefficient of glass if its content is more than 3%, and therefore, TiO in the present invention2Content For 3% hereinafter, preferably 0~2%, more preferably 0~1%.In some embodiments, can include about 0%, be greater than 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3% TiO2。
Nb2O5、WO3Belong to high-refraction high-dispersion oxide, is added to the refractive index and color of adjustable glass in glass It dissipates, while promoting the chemical stability of glass.Through inventor the study found that in this system glass, both oxides are promoted The ability of glass refraction temperature coefficient is slower than other high-refraction high-dispersion oxides, such as TiO2、Bi2O3、Ta2O5, PbO etc..From For the angle for reducing glass refraction temperature coefficient of the present invention, both high dispersion oxides are the ideals for increasing glass dispersion Oxide.If Nb2O5Content be more than 5%, the Abbe number of glass can rapid decrease design requirement, the anti-crystallization of glass is not achieved Performance also can rapid decrease, therefore, the present invention in Nb2O5Content be limited to 5% or less.If Nb2O5Content be lower than 0.1%, It means that needing to be added more WO3Or other above-mentioned high dispersion oxides, it will lead to the transmitance of glass in this way Decline or thermal refractive index coefficient rapid increase, therefore, Nb2O5Content be preferably 0.1~5%, more preferably 0.5~ 4%, further preferably 1~3%.In some embodiments, can include about 0%, be greater than 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3% Nb2O5。
WO3Nb can be substituted on a small quantity2O5It uses, if but its content is more than 2%, and the transmitance of glass can be decreased obviously.Cause This, content be limited to 2% hereinafter, preferably 1% hereinafter, further preferably do not introduce.In some embodiments, it can wrap Containing about 0%, be greater than 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2% WO3。
Further, glass of the present invention mainly uses under outdoor adverse circumstances, such as on-vehicle lens, security protection Camera lens etc., can be for a long time by solar exposure, especially in highlands.Traditional optical glass is designed towards photographic goods , usually not consider glass after being exposed to the sun for a long time the problem of transmitance decline.Therefore, the resistance to sunshine for how promoting glass is steady It is qualitative, it is an Important Problems of glass concern of the present invention.
It is found through inventor's test of many times, in some embodiments, Nb2O5And TiO2Use simultaneously can be than being used alone TiO2The effect for promoting the resistance to sunshine stability of glass becomes apparent from.But work as TiO2With Nb2O5Ratio TiO2/Nb2O5When greater than 1, The resistance to sunshine stability of glass is no longer promoted, but thermal refractive index coefficient rises very fast, this is to wanting to obtain lower refractive index temperature The target of degree coefficient is disagreed.Therefore, in order to obtain more low-refraction temperature coefficient and the strong glass of resistance to sunshine stability, TiO2/Nb2O5Value be 1 hereinafter, preferably 0.8 hereinafter, further preferably 0.5 or less.In some embodiments, TiO2/ Nb2O5Value can for 0,0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,0.65,0.7, 0.75、0.8、0.85、0.9、0.95、1。
For the glass of system of the present invention, ZnO is added in glass the chemical stability that can promote glass, reduces glass High temperature viscosity, to reduce the production difficulty of glass.But inventor is the study found that if the content of ZnO is more than 5%, glass Thermal refractive index coefficient can rapid decrease.Therefore, content be limited to 5% hereinafter, preferably 3% hereinafter, further preferably Not introduce.In some embodiments, can include about 0%, be greater than 0%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% ZnO.
BaO, CaO, SrO, MgO are alkaline earth oxide, be added in glass the refractive index of adjustable glass and Dispersion, the stability of reinforcing glass promote the devitrification resistance energy of glass.General technical literature thinks of the same clan in such glass The effect of oxide is essentially identical.But inventor is had found by test of many times, and this system glass is paid close attention to the most Thermal refractive index coefficient, chemical stability, for devitrification resistance energy, the effect of above several alkaline earth oxides exists very Big difference.
The ability that BaO reduces glass refraction temperature coefficient is most strong, therefore its content need to be limited to 10% or more, Cai Nengda To the desired thermal refractive index coefficient of invention；If but its content is more than 40%, the chemical stability of glass, especially water resistance meeting Rapid decrease, the devitrification resistance of glass can also can rapid decreases.Therefore its content be limited to 10~40%, preferably 12~ 35%, further preferably 15~32%.In some embodiments, can include about 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40% BaO.
The ability that SrO reduces glass refraction temperature coefficient is better than CaO but is weaker than BaO, is added in glass and destroys glass The ability of chemical stability is weaker than BaO, if the content of SrO is more than 15%, the devitrification resistance of glass can instead can high progression, together When glass thermal refractive index coefficient can rapid increase, therefore its content be 15% or less.On the other hand, it is ground by many experiments Study carefully discovery, when BaO is higher than 15%, the SrO of 0.5% or more addition can be obviously improved the water resistance of glass and anti-crystallization is stablized Property, while the thermal refractive index coefficient of glass will not also obviously rise.Therefore, the present invention in preferably SrO content be 0.5~ 15%, more preferably 1~12%, further preferably 1.5~10%.In some embodiments, it can include about 0%, be greater than 0%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15% SrO.
Generally, CaO is essential component in lanthanum crown glass, and the refraction of glass can be promoted by being added in glass Rate and dispersion significantly reduce the density of glass, so that eyeglass can reduce the high temperature viscosity and surface tension of glass with lightweight, Reduce the production difficulty of glass.But for system glass of the present invention, CaO reduces the thermal refractive index coefficient of glass Ability is inferior to BaO and SrO, therefore from the perspective of reducing thermal refractive index coefficient, does not introduce preferably.But CaO with In upper three kinds of alkaline earth oxides, the ability for destroying water resistance is most weak, therefore from the perspective of promoting glass water resistance, It can add in right amount.Therefore, CaO content is limited to 0~10%, preferably 0~8%, further preferably 0~6%.? In some embodiments, can include about 0%, be greater than 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% CaO.
For system glass of the present invention, MgO is harmful to glass refraction temperature coefficient is reduced, but a small amount of addition The water resistance and stability of glass can be promoted.If its content is more than 5%, design, which is not achieved, in the thermal refractive index coefficient of glass is wanted It asks, while the anti-crystallization ability of glass can rapid decrease.Therefore, content is limited to 5% hereinafter, preferably 3% hereinafter, into one Step does not introduce preferably.In some embodiments, can include about 0%, be greater than 0%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% MgO.
Importantly, inventor is the study found that in some embodiments, when tri- kinds of alkaline-earth metal of BaO, CaO, SrO When oxide all adds, complicated synergistic effect can occur for glass, and performance is not as linear become occurs for the addition of single substance Change, when the value of CaO/ (BaO+SrO) is more than 0.5, although the chemical stability of glass has certain promotion, the refraction of glass Rate temperature coefficient can rapid increase, the devitrification resistance of glass can rapid decrease, therefore in the present invention CaO/ (BaO+SrO) value Preferably 0~0.5.In some embodiments, the value of more preferable CaO/ (BaO+SrO) is 0.01~0.4, further preferably When 0.02~0.3, the thermal refractive index coefficient of glass, chemical stability, devitrification resistance can reach expected design.Some In embodiment, the value of CaO/ (BaO+SrO) can be 0, be greater than 0,0.01,0.02,0.05,0.1,0.15,0.2,0.25,0.3, 0.35、0.4、0.45、0.5。
In some embodiments, if wanting to obtain lower temperature specific refractivity, BaO content >=CaO content is preferably satisfied, Further satisfaction SrO content >=CaO content further meets BaO content >=SrO content >=CaO content.
If adding the chemical stability that ZnO carrys out reinforcing glass in glass system, just must take into account brought by addition ZnO The problem of thermal refractive index coefficient rises.Inventor the study found that in some embodiments, ZnO/'s (CaO+BaO+SrO) The chemical stability of value meeting refractive index temperature coefficient and glass has an impact.When the value of ZnO/ (CaO+BaO+SrO) is greater than 0.3 When, the chemical stability of glass almost no longer increases, but the thermal refractive index coefficient of glass steeply rises.Therefore, to acquisition Chemical stability is preferable and the lower glass of thermal refractive index coefficient, the value of ZnO/ (CaO+BaO+SrO) should be preferably 0.3 with Under, more preferably 0.2 hereinafter, further preferably 0.15 or less.In some embodiments, ZnO/ (CaO+BaO+SrO) Value can be 0, be greater than 0,0.01,0.02,0.03,0.04,0.05,0.06,0.07,0.08,0.09,0.1,0.11,0.12, 0.13、0.14、0.15、0.16、0.17、0.18、0.19、0.2、0.21、0.22、0.23、0.24、0.25、0.26、0.27、 0.28、0.29、0.3。
Li2O、Na2O、K2O belongs to alkali metal oxide, and proper amount of addition can reduce the refractive index temperature system of glass Number, but the chemical stability of glass, devitrification resistance can quickly reduce.Inventor is had found by a large number of experiments:
1) in system glass of the present invention, the thermal refractive index coefficient of glass be not with alkali metal oxide increase and Linear reduction, but no longer decline to thermal refractive index coefficient after an extreme value, but continue to add alkali gold in this extreme value Belong to oxide, the devitrification resistance of glass can sharply deteriorate.In some embodiments, Li2O、Na2O and K2The sum of content of O Li2O+Na2O+K2If the value of O, more than 8%, the thermal refractive index coefficient of glass simultaneously no longer declines, and devitrification resistance energy and water resistance Sharply decline.
For the angle of production, it is expected that high temperature viscosity is lower in clarification, be more conducive to the discharge of bubble, therefore, if When thermal refractive index coefficient, water resistance and the devitrification resistance of glass can reach design requirement, it can add above-mentioned no more than 8% Alkali metal oxide promotes the high temperature viscosity of glass, and the bubble degree of glass is horizontal when promoting volume production.Therefore, Li2O+Na2O+K2O Total amount control 8% hereinafter, it is preferred that 6% hereinafter, further preferably below 5%.In some embodiments, Li2O +Na2O+K2The total amount of O can be about 0%, is greater than 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%.
2) in the presence of three of the above alkali metal oxide is all common, synergistic effect can be generated, in some embodiments, If Li2O/(K2O+Na2O when value) is greater than 0.5, the thermal refractive index coefficient of glass is basically unchanged, but the devitrification resistance energy of glass Sharply decline with chemical stability, therefore, Li2O/(K2O+Na2O value) is preferably smaller than 0.5, and more preferably less than 0.4, further Preferably smaller than 0.3.In some embodiments, Li2O/(K2O+Na2O value) can for 0, be greater than 0,0.01,0.02,0.03, 0.04、0.05、0.06、0.07、0.08、0.09、0.1、0.15、0.2、0.25、0.3、0.35、0.4、0.45、0.5。
Inventor's research also found, for the angle for reducing thermal refractive index coefficient, K2O and Na2O is stronger, and Li2O times It；For the angle of chemical stability for destroying glass, K2O and Na2O is stronger, and Li2O takes second place；From the anti-analysis for destroying glass For brilliant aspect of performance, Li2O is most strong, K2O and Na2O takes second place.Therefore, in order to obtain the refractive index temperature system for meeting expected design How number, chemical stability and devitrification resistance energy, select suitable species and proper amount of alkali metal oxide, needs a large amount of Experimental study determines.For the alkali metal oxide of one pack system, if Na2O content is more than 8%, the devitrification resistance energy of glass Can sharply it decline with chemical stability, therefore, in some embodiments, content is limited to 0~8%, preferably 0.5~ 6%, further preferably 1~3%.In some embodiments, if K2O content is higher than 6%, the devitrification resistance energy of glass and change Learn stability can rapid decrease, therefore, content is limited to 0~6%, preferably 0.3~4%, further preferably 0.5~ 3%.In some embodiments, Li2If the content of O more than 5%, the devitrification resistance of glass can rapid decrease, therefore it contains Amount preferably 5% hereinafter, more preferable 3% hereinafter, further preferably do not introduce.In some embodiments, Li2The content of O It can be about 0%, be greater than 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%.In some realities It applies in mode, Na2The content of O can be about 0%, is greater than 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%.In some embodiments, K2The content of O can be about 0%, Greater than 0%, 0.3%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%.
The discovery of inventor's numerous studies, in some embodiments, Na in glass2O/K2Bubble degree of the ratio of O with glass There is biggish association with water resistance, works as Na2O/K2When the value of O is greater than 5.0, the water resistance of glass sharply declines；Work as Na2O/K2O's When value is less than 0.2, the bubble degree rapid decrease of glass.Therefore, Na2O/K2The value of O is between 0.2~5.0, preferably 0.3~ Between 4.0, when between further preferably 0.4~3.0, glass can get excellent bubble degree and water resistance.In some implementations In mode, Na2O/K2The value of O can for 0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.2,1.4,1.5,1.6, 1.8、2.0、2.2、2.4、2.5、2.6、2.8、3.0、3.2、3.4、3.5、3.6、3.8、4.0、4.2、4.4、4.5、4.6、4.8、 5.0。
For system glass of the present invention, the total content and La of the alkaline earth oxides such as BaO, SrO, CaO2O3、 Gd2O3、Y2O3The ratio of total content and thermal refractive index coefficient, devitrification resistance energy and the water resistance of glass have it is biggish Relationship.In some embodiments, as (BaO+SrO+CaO)/(La2O3+Gd2O3+Y2O3) value be greater than 2.5 when, the folding of glass The rate temperature coefficient of penetrating no longer declines, and the water resistance rapid decrease of glass；As (BaO+SrO+CaO)/(La2O3+Gd2O3+Y2O3) When less than 0.7, the water resistance of glass is promoted, but the thermal refractive index coefficient rapid increase of glass, the devitrification resistance of glass It can rapid decrease.Therefore, it is lower to obtain thermal refractive index coefficient, water resistance reaches design requirement, and devitrification resistance can be compared with Good glass needs to meet (BaO+SrO+CaO)/(La2O3+Gd2O3+Y2O3) value be 0.7~2.5, preferably 0.8~2.3, Further preferably 0.9~2.1.In some embodiments, (BaO+SrO+CaO)/(La2O3+Gd2O3+Y2O3) value can be 0.7、0.8、0.9、1.0、1.1、1.2、1.3、1.4、1.5、1.6、1.7、1.8、1.9、2.0、2.1、2.2、2.3、2.4、2.5。
In system glass of the present invention, BaO and La2O3It is main component, the study found that folding of its ratio for glass The water resistance and its devitrification resistance for penetrating rate temperature coefficient and glass can have biggish association.In some embodiments, when BaO, La2O3The ratio BaO/La of content2O3When greater than 2, the thermal refractive index coefficient of glass no longer declines, but glass is water-fast impatient Play decline；Work as BaO/La2O3Value less than 0.6 when, although the water resistance of glass has biggish promotion, but the refractive index temperature of glass Design requirement is not achieved in degree coefficient, and the devitrification resistance of glass can sharply deteriorate, or even crystallization just occurs in fusion process.Cause This, BaO/La2O3Value be limited between 0.6~2, preferably 0.65~1.9, further preferably 0.7~1.8.In some realities It applies in mode, BaO/La2O3Value can for 0.6,0.65,0.7,0.75,0.8,0.85,0.9,0.95,1.0,1.05,1.1, 1.15、1.2、1.25、1.3、1.35、1.4、1.45、1.5、1.55、1.6、1.65、1.7、1.75、1.8、1.85、1.9、1.95、 2.0。
Inventor is the study found that in some embodiments, (CaO+BaO+SrO)/(Al2O3+ZrO2+TiO2) value and The thermal refractive index coefficient of glass has biggish association.As (CaO+BaO+SrO)/(Al2O3+ZrO2+TiO2) value less than 8 when, Although the chemical stability and devitrification resistance of glass can have faint promotion, the thermal refractive index coefficient of glass is steeply risen, Design requirement is not achieved.Therefore, (CaO+BaO+SrO)/(Al2O3+ZrO2+TiO2) value should be greater than 8, preferably greater than 10, into one Step preferably greater than 12.
Sb2O3、SnO2, SnO and CeO2One or more of component can be used as clarifying agent addition, by adding on a small quantity Sb2O3、SnO2、CeO2The clarifying effect of glass can be improved in component, but works as Sb2O3When content is more than 2%, glass has Clarification Performance Reduced tendency, simultaneously because its strong oxidation promotes the deterioration of shaping dies, therefore Sb of the present invention2O3Additive amount be 2% hereinafter, preferably 1% hereinafter, more preferably 0.5% or less.SnO2, SnO can also be used as clarifying agent to add, but work as its When content is more than 2%, glass can be coloured, or when heat, soften glass and carry out die forming etc. shape again when, Sn can be at For the starting point that nucleus generates, the tendency of devitrification, therefore SnO of the invention are generated2With the difference content of SnO be 2% hereinafter, it is preferred that For 1% hereinafter, more preferably 0.5% hereinafter, do not introduce further preferably.CeO2Effect and additive amount ratio and SnO2Unanimously, Its content is 2% hereinafter, preferably 1% hereinafter, more preferably 0.5% hereinafter, not introducing further preferably.In some embodiment party In formula, one of above 4 kinds of clarifying agents or more than one content be about 0%, be greater than 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%.
In some embodiments, As can also be used2O3, the compound of Cl, the compound of Br etc. be used as clarifying agent, contain Amount be respectively 2% hereinafter, preferably 1% hereinafter, more preferably 0.5% hereinafter, but from the factors such as environmental protection consider, preferably do not introduce As2O3.In some embodiments, one of above 3 kinds of clarifying agents or more than one content be about 0%, be greater than 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%.
[about the ingredient that should not contain]
In the range of not damaging glass performance of the invention, can add as needed other above-mentioned not referred at Point.But the transiting metal components 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 light region generates absorption, so that weakening raising of the invention can The property of light-exposed transmitance effect, therefore it is desirable, especially for the optical glass that the transmitance of visible light region wavelength requires, excellent Choosing does not include actually.
The cation of Pb, Th, Cd, Tl, Os, Be and Se have control to use as harmful chemical substance in recent years Tendency, not only in the manufacturing process of glass, until the measure in disposition after manufacturing procedure and commercialization to environmental protection It is required.Therefore, in the case where paying attention to the influence to environment, other than being inevitably mixed into, preferably actually not Contain them.Optical glass becomes the substance for not including pollution environment actually as a result,.Therefore, even if not taking special ring Measure in the countermeasure of border, optical glass of the invention are also able to carry out manufacture, processing and discard.
" not introducing " " not containing " " 0% " described herein refers to not deliberately by the compound, molecule or element etc. It is added in optical glass of the present invention as raw material；But as the raw material and/or equipment of production optical glass, can exist certain It is not the impurity deliberately added or component, a small amount of or trace can contains in final optical glass, such situation is also in this hair In the protection scope of bright patent.
In the following, being illustrated to the performance of optical glass of the invention.
[refractive index and Abbe number]
Optical glass refractive index (nd) and Abbe number (νd) tested according to 7962.1-2010 prescriptive procedure of GB/T.
The range of optical glass refractive index (nd) of the present invention is 1.65~1.73, and preferred range is 1.67~1.72；This Abbe number (the ν of invention glassd) range be 47~55, preferred scope be 48~52.
[thermal refractive index coefficient]
According to 7962.4-2010 prescriptive procedure of GB/T, the refractive index temperature in 20~40 DEG C of range of optical glass is tested Coefficient (d line dn/dt relative (10-6/ DEG C))
Temperature coefficient of optical glass refractive index (dn/dt) of the present invention is≤0, preferably≤- 0.5, more preferably≤- 1.0, Further preferably≤- 2.0.
[water-fast effect stability]
Optical glass is water-fast effect stability Dw(powder method) is tested according to 17129 prescriptive procedure of GB/T.
The water-fast effect stability D of optical glass of the present inventionwFor 4 classes and its more than, preferably 3 classes and its more than, more preferably For 2 classes and its more than.
[bubble degree]
The bubble degree of optical glass is tested by GB/T7962.8-2010 prescriptive procedure.
Optical glass bubble degree of the present invention is A grades or more, preferably A0Grade or more, more preferably A00Grade.
[striped degree]
The striped degree of glass of the present invention is measured by method as defined in MLL-G-174B.Method is with point light source and lens The schlieren instrument of composition, from the direction for being easiest to see striped, and standard sample audit by comparison is divided into 4 grades, respectively A, B, C, D grades, the A grades of stripeds to be visible by naked eyes under regulation testing conditions, B grades are to have item that is thin and dispersing under regulation testing conditions Line, C grades are to have slight parallel stripes under regulation testing conditions, and D grades are to have rough striped under regulation testing conditions.
The striped of optical glass of the invention is C grades or more, preferably B grades or more, more preferably A grades.
[resistance to sunshine performance]
The optical glass stability of resistance to sunshine is pressed under JOGIS04-1994 standard conditions, 10mm thickness sample irradiation 4 hours, is led to The spectral transmittance curve before comparing irradiation and after irradiation is crossed, determines glass in the attenuation of 400nm wave band.The spectrum of glass Transmittance curve uses spectrophotometer measurement.
The resistance to sunshine stability of optical glass of the present invention is that transmitance decline is no more than 10% at 400nm wavelength, is not preferably surpassed 8% is crossed, is further preferably no more than 5%.
[devitrification resistance energy]
The devitrification resistance energy test method of optical glass are as follows: mother glass is cut into 20 × 20 × 10mm specification, is put into Temperature is Tg30 minutes are kept the temperature in+230 DEG C of Muffle furnace, Xu Leng in heat-preservation cotton is put into after taking-up, observes Surface Crystallization after cooling Situation.
The mother glass of optical glass of the present invention is cut into 20 × 20 × 10mm specification, and being put into temperature is Tg+ 230 DEG C of horse 30 minutes not are kept the temperature in furnace, Xu Leng in heat-preservation cotton is put into after taking-up, surface is without obvious crystallization.Surface of the present invention is without obvious Crystallization refers to: there is crystallization spot on surface without crystallization spot or surface, but its area accounts for 5% or less and crystallization depth of entire area not More than 0.5mm.
In the following, gas preform and optical element that description is of the invention.
Gas preform and optical element of the invention is formed by the optical glass of aforementioned present invention.Glass of the invention Prefabricated component has medium refractive index and lower thermal refractive index coefficient characteristic；Optical element of the invention have medium 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.
Since optical glass of the present invention has the performances such as excellent chemical stability and lower thermal refractive index coefficient, especially It is suitably applied the fields such as vehicle-mounted, monitoring security protection.
In order to further appreciate that technical solution of the present invention, the embodiment of optical glass of the present invention is described below.It should It is noted that there is no limit the scope of the present invention for these embodiments.
[optical glass embodiment]
The optical glass (Examples 1 to 2 0) shown in table 2~3 is by the ratio according to each embodiment shown in table It weighs and hybrid glass is with common raw material (such as oxide, hydroxide, carbonate, nitrate), mixed raw material is placed on In platinum crucible, melt 2.5~4 hours in 1300~1350 DEG C, and after clarified, stirring and homogenizing, obtains not gas Bubble and the homogeneous melt glass without undissolved substance casting mold and anneal this melten glass in mold.
Examples 1 to 20 shows optical glass composition and refractive index (nd)；Abbe number (νd)；Within the scope of 20~40 DEG C, Thermal refractive index coefficient (d line dn/dt relative (10-6/℃))(dn/dt)；Powder method is water-fast effect stability (Dw)；It will Mother glass is cut into 20 × 20 × 10mm specification, and being put into temperature is Tg30 minutes are kept the temperature in+230 DEG C of Muffle furnace, after taking-up It is put into Xu Leng in heat-preservation cotton, observes Surface Crystallization situation after cooling, no obvious crystallization is denoted as " A ", has obvious crystallization to be denoted as " B "； Bubble degree, striped degree are provided to indicate by standard；After resistance to sunshine stability test, transmitance decline hundred at 400nm wavelength Rate is divided to be indicated with " Δ T (%) ".
SiO2/B2O3Value indicated with K1；TiO2/Nb2O5Value indicated with K2；The value of CaO/ (BaO+SrO) is indicated with K3； The value of ZnO/ (CaO+BaO+SrO) is indicated with K4；Li2O+Na2O+K2The total amount of O is indicated with K5；Li2O/(K2O+Na2O value) It is indicated with K6；Na2O/K2O value is indicated with K7；(BaO+SrO+CaO)/(La2O3+Gd2O3+Y2O3) value indicated with K8；BaO/ La2O3Value indicated with K9；(CaO+BaO+SrO)/(Al2O3+ZrO2+TiO2) value indicated with K10.
Table 2
Table 3
[gas preform embodiment]
The obtained optical glass of Examples 1 to 10 in table 2 is cut into predefined size, then is equably coated on the surface Then release agent is heated, softens, is press-formed, make recessed meniscus shaped lens, male bend moon-shaped lens, biconvex lens, The prefabricated component of the various lens such as biconcave lens, plano-convex lens, plano-concave lens, prism.
[optical element embodiment]
By obtained these prefabricated components annealing of above-mentioned gas preform embodiment, while reducing inside glass deformation It is finely adjusted, so that the optical characteristics such as refractive index reach desirable value.
Then, each prefabricated component is ground, ground, make recessed meniscus shaped lens, male bend moon-shaped lens, biconvex lens, The various lens such as biconcave lens, plano-convex lens, plano-concave lens, prism.Antireflection can be also coated on the surface of gained optical element Film.

Claims (18)

1. optical glass, which is characterized in that it includes SiO that it, which is formed,2、B2O3、La2O3, RO and Rn2O, wherein R0 be MgO, CaO, One of SrO and BaO or more than one, Rn20 is Li2O、K2O and Na2One of O or more than one, the refractive index of glass It is 1.65~1.73, Abbe number is 47~55, and thermal refractive index coefficient is≤0.
2. optical glass as described in claim 1, which is characterized in that it is formed in terms of weight percentage, is contained: SiO2: 4 ~20%, B2O3: 10~30%, La2O3: 10~35%, BaO:10~40%, SrO:0~15%, CaO:0~10%, MgO:0 ~5%, Li2O:0~5%, K2O:0~6%, Na2O:0~8%, Gd2O3: 0~8%, Y2O3: 0~5%, ZrO2: 0~3%, Al2O3: 0~3%, TiO2: 0~3%, Nb2O5: 0~5%, WO3: 0~2%, ZnO:0~5%, clarifying agent: 0~2%.
3. optical glass, which is characterized in that it is formed in terms of weight percentage, is contained: SiO2: 4~20%, B2O3: 10~ 30%, La2O3: 10~35%, BaO:10~40%, SrO:0~15%.
4. optical glass as claimed in claim 3, which is characterized in that also contain: CaO:0~10%, MgO:0~5%, Li2O: 0~5%, K2O:0~6%, Na2O:0~8%, Gd2O3: 0~8%, Y2O3: 0~5%, ZrO2: 0~3%, Al2O3: 0~3%, TiO2: 0~3%, Nb2O5: 0~5%, WO3: 0~2%, ZnO:0~5%, clarifying agent: 0~2%.
5. optical glass, which is characterized in that it is formed in terms of weight percentage by SiO2: 4~20%, B2O3: 10~30%, La2O3: 10~35%, BaO:10~40%, SrO:0~15%, CaO:0~10%, MgO:0~5%, Rn20:0~8%, Gd2O3: 0~8%, Y2O3: 0~5%, ZrO2: 0~3%, Al2O3: 0~3%, TiO2: 0~3%, Nb2O5: 0~5%, WO3: 0 ~2%, ZnO:0~5% is formed, wherein Rn20 is Li2O、K2O、Na2One of O or more than one.
6. the optical glass as described in Claims 1 to 5 any claim, which is characterized in that SiO2/B2O3It is 0.4~1.3, Preferably 0.45~1.2, more preferably 0.5~1.1；And/or BaO/La2O3It is 0.6~2, preferably 0.65~1.9, more preferably It is 0.7~1.8.
7. the optical glass as described in Claims 1 to 5 any claim, which is characterized in that CaO/ (BaO+SrO) be 0~ 0.5, preferably 0.01~0.4, more preferably 0.02~0.3；And/or ZnO/ (CaO+SrO+BaO) is 0~0.3, preferably 0 ~0.2, more preferably 0~0.15；And/or (CaO+SrO+BaO)/(La2O3+Gd2O3+Y2O3) it is 0.7~2.5, preferably 0.8 ~2.3, more preferably 0.9~2.1；And/or (CaO+SrO+BaO)/(Al2O3+ZrO2+TiO2) it is greater than 8, preferably greater than 10, more Preferably greater than 12；And/or SrO content >=CaO content, preferably BaO content >=SrO content >=CaO content.
8. the optical glass as described in Claims 1 to 5 any claim, which is characterized in that Li2O+Na2O+K2O be 0~ 8%, preferably 0~6%, more preferably 0~5%；And/or Li2O/(K2O+Na2It O) is 0~0.5, preferably 0~0.4, it is more excellent It is selected as 0~0.3；And/or Na2O/K2O is 0.2~5.0, preferably 0.3~4.0, more preferably 0.4~3.0；And/or TiO2/ Nb2O5For 1 hereinafter, preferably 0.8 hereinafter, more preferably 0.5 or less.
9. the optical glass as described in Claims 1 to 5 any claim, which is characterized in that it is formed with weight percent It indicates, contains: SiO2: 6~18%, and/or B2O3: 12~25%, and/or La2O3: 12~30%, and/or BaO:12~ 35%, and/or SrO:0.5~15%, and/or CaO:0~8%, and/or Gd2O3: 1~6%, and/or Y2O3: 0~3% and/ Or ZrO2: 0.1~3%, and/or Al2O3: 0~2%, and/or TiO2: 0~2%, and/or Nb2O5: 0.1~5%, and/or WO3: 0~1%, and/or ZnO:0~3%, and/or MgO:0~3%, and/or Li2O:0~3%, and/or K2O:0.3~4%, And/or Na2O:0.5~6%.
10. the optical glass as described in Claims 1 to 5 any claim, which is characterized in that it is formed with weight percent It indicates, contains: SiO2: 8~16%, and/or B2O3: 15~22%, and/or La2O3: 15~28%, and/or BaO:15~ 32%, and/or SrO:1~12%, and/or CaO:0~6%, and/or Gd2O3: 1~4%, and/or Y2O3: 1~3%, and/or ZrO2: 0.1~2%, and/or Al2O3: 0.1~1%, and/or TiO2: 0~1%, and/or Nb2O5: 0.5~4%, and/or K2O:0.5~3%, and/or Na2O:1~3%.
11. the optical glass as described in Claims 1 to 5 any claim, which is characterized in that it is formed with weight percent It indicates, contains: ZrO2: 0.1~1%, and/or Nb2O5: 1~3%, and/or SrO:1.5~10%.
12. the optical glass as described in Claims 1 to 5 any claim, which is characterized in that the refractive index of glass is 1.65 ~1.73, preferably 1.67~1.72；Abbe number is 47~55, preferably 48~52.
13. the optical glass as described in Claims 1 to 5 any claim, which is characterized in that the refractive index temperature system of glass Number is≤0, preferably≤- 0.5, more preferably≤- 1.0, further preferably≤- 2.0.
14. the optical glass as described in Claims 1 to 5 any claim, which is characterized in that the water-resistant stability of glass is 4 classes and its more than, preferably 3 classes and its more than, more preferably 2 classes and its more than；And/or bubble degree is A grades or more, preferably A0Grade or more, more preferably A00Grade；And/or striped is C grades or more, preferably B grades or more, more preferably A grades；And/or resistance to sunshine Stability is that transmitance decline is no more than 10%, preferably more than 8% at 400nm wavelength, is further preferably no more than 5%.
15. gas preform is made of optical glass described in claim 1~14 any claim.
16. optical element, using described in optical glass described in claim 1~14 any claim or claim 15 Gas preform is made.
17. optical instrument, using described in optical glass described in claim 1~14 any claim or claim 16 Optical element is made.
18. optical element described in optical glass described in claim 1~14 any claim or claim 16 is in vehicle Application in load.
CN201811391994.9A 2018-11-21 2018-11-21 Optical glass, glass preform, optical element and optical instrument Active CN109205616B (en)

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