CN101215082A - Optical glass with high refractive index - Google Patents

Optical glass with high refractive index Download PDF

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Publication number
CN101215082A
CN101215082A CNA2007100512160A CN200710051216A CN101215082A CN 101215082 A CN101215082 A CN 101215082A CN A2007100512160 A CNA2007100512160 A CN A2007100512160A CN 200710051216 A CN200710051216 A CN 200710051216A CN 101215082 A CN101215082 A CN 101215082A
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glass
refractive index
high refractive
optical glass
composition
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陈艳丽
李克炎
张卫
沈义梅
邓和平
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Hubei New Huaguang Information Materials Co Ltd
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Hubei New Huaguang Information Materials Co Ltd
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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
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
    • C03C3/155—Silica-free oxide glass compositions containing boron containing rare earths containing zirconium, titanium, tantalum or niobium

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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)
  • Glass Compositions (AREA)

Abstract

The invention is an optical glass with high refractive index, which belongs to the technical field of optical glass. The invention mainly resolves the problems that the refractive index of the exsisting optical glass is not high enough or the transforming temperature is not low enough though the refractive index is high enough. The common glass of the invention is characterized in that the invention has the following weight percentage of oxide, 0-5% SiO2, 15-30% B2O3, 0-3% Al2O3, 20-40% La2O3, 0-6% Y2O3, 0-10% Gd2O3, 0-6% Yb2O3, 1-10% TiO2, 3-10% ZrO2, 10-30% Nb2O5, 0-20% Ta2O3, 1-10% WO3, 1-25% ZnO, 0-6% CaO, 0-3% Li2O, 0-0.5% Sb2O3, the glass with low transforming temperature is characterized in that apart from the components of 1-5% WO3 and 8-25% ZnO, the rest components are the same as the above scheme. The refractive index (nd) of the invention is between 1.89-1.91, and the abbe coefficient (vd) is with the range of 30-32. The invention is further equipped with a lower transforming temperature (Tg), and is mainly applied for small size lens glass which needs high refractive index.

Description

Optical glass having high refractive index
Technical field
Invention belongs to the opticglass technical field, is specifically related to a kind of specific refractory power (n d) between 1.89～1.91, Abbe number (υ d) in 30～32, objectionable constituent such as thoriated, lead, arsenic not, the glass coloring degree is little, good stability, the high refractive index optics glass that is suitable for producing in batches.
Background technology
Be accompanied by a large amount of uses of digital camera and camera mobile phone, small-sized camera lens demand sharply increases, and is applicable to that the glass of high refractive index demand of producing small-sized camera lens also along with increase, particularly is suitable for the glass of high refractive index of compression molding.Such a glass of high refractive index, publication number is that the Chinese invention patent application prospectus of CN1569706A has been announced a kind of SiO 2-B 2O 3-BaO-La 2O 3-TiO 2-Nb 2O 5The optical glass of system, this glass is because SiO 2, BaO with the metering bigger, transition temperature (T g) height, be unwell to compression molding, and because of TiO 2Content height and coloring is stronger.Granted publication number has been announced a kind of at B for the Chinese invention patent specification of CN1182058C 2O 3-La 2O 3-Ta 2O 5-Gd 2O 3Add Nb in the system 2O 5Deng glass of high refractive index because Ta 2O 5Use amount is bigger, the cost height, and the ZnO use amount is low, and just ordinary optical glass not too is suitable for compression molding.Be that the Chinese invention patent application prospectus of CN1663923A has been announced a kind of at B at publication number 2O 3-La 2O 3-Gd 2O 3Glass transformation temperature (T in the-ZnO system g) in 600～640 ℃ of scopes, although be suitable for compression molding, WO 3Content is very high, surpasses 10%, causes easily the molded piece surface line to occur bursting in the compression molding process, and bigger to the corrosion function of mould, so WO 3Suitable content should be below 5%.Publication number is that the Chinese invention patent application prospectus of CN1663923A has announced that a kind of lanthanum dense flint glass adopts at B 2O 3-La 2O 3-TiO 2-Nb 2O 5Imported ZrO in the system 2Deng reaching high index of refraction, ZnO content is lower in this system, does not contain WO 3Deng composition, be common optical glass, do not possess transition temperature (T g) low characteristics.Publication number is that the Chinese invention patent application prospectus of CN1524815A has been announced a kind of at SiO 2-B 2O 3-La 2O 3-Nb 2O 5-TiO 2Add BaO, TiO in the system 2Deng reaching high index of refraction, but ZnO content is lower in forming, WO 3Content is very low or do not have Li 2O content is very low or do not have, and belongs to common glass of high refractive index, does not possess transition temperature (T g) low characteristics.
Summary of the invention
Purpose of the present invention provides a kind of specific refractory power (nd) between 1.89～1.91 at above-mentioned weak point exactly, Abbe number (υ d) in 30～32, objectionable constituent such as thoriated, lead, arsenic not, and the glass coloring degree is little, good stability, the common glass of high refractive index that is suitable for producing in batches.
Further aim of the present invention provides a kind of transition temperature (T g) low, be suitable for the glass of high refractive index of compression molding.
The technical solution of the common optical glass having high refractive index of the present invention is: a kind of optical glass having high refractive index is characterized in that: its compositional range contains by oxide weight percentage: SiO 20～5%, B 2O 315～30%, Al 2O 30～3%, La 2O 320～40%, Y 2O 30～6%, Gd 2O 30～10%, Yb 2O 30～6%, TiO 21～10%, ZrO 23～10%, Nb 2O 510～30%, Ta 2O 30～20%, WO 31～10%, ZnO1～25%, CaO0～6%, Li 2O0～3%, Sb 2O 30～0.5%.Glass in this compositing range has specific refractory power (nd) between 1.89～1.91 and Abbe number (υ d) 30～32 with interior optics glass.
Common optical glass having high refractive index is SiO 2-B 2O 3-La 2O 3-ZnO-Nb 2O 5-TiO 2-WO 3-ZrO 2Glass system mainly is the TiO that uses small amount in prescription 2Reach the suitable atmosphere control of founding and allow glass have lower degree of staining, glass has good chemical stability simultaneously, and crystallization property is good, is suitable for batch production.
The technical solution of the low transition temperature optical glass having high refractive index of the present invention is: a kind of optical glass having high refractive index is characterized in that: its compositional range contains by oxide weight percentage: SiO 20～5%, B 2O 315～30%, Al 2O 30～3%, La 2O 320～40%, Y 2O 30～6%, Gd 2O 30～10%, Yb 2O 30～6%, TiO 21～10%, ZrO 23～10%, Nb 2O 510～30%, Ta 2O 30～20%, WO 31～5%, ZnO8～25%, CaO0～6%, Li 2O0～3%, Sb 2O 30～0.5%.Its unique point of glass in this compositing range is, contains ZnO, WO in the composition 3, Li 2O, and the content of ZnO higher (ZnO8～25%), WO 3Content is less than 5% and greater than 1% (WO 31～5%), such glass has lower transition temperature (T g), be suitable for compression molding.Glass in this compositing range also has specific refractory power (nd) between 1.89～1.91 and Abbe number (υ d) 30～32 with interior optics glass.
Low transition temperature optical glass having high refractive index is SiO 2-B 2O 3-La 2O 3-ZnO-Nb 2O 5-TiO 2-WO 3-ZrO 2-Gd 2O 3(or Y 2O 3)-Li 2O is by using relatively large ZnO and a certain amount of WO 3, Li 2O etc. reduce the transition temperature of glass, use simultaneously the TiO of small amount in prescription 2And the suitable atmosphere control of founding allows the degree of staining of glass reduce.Thereby obtained high refractive index and possessed transition temperature (T g) the low and low glass of degree of staining, and having excellent chemical stability, crystallization property is good, is suitable for producing in batches.
Optical glass having high refractive index contains Li in forming 2O, Nb 2O 5, WO 3, found atmosphere by change, can reach degree of staining preferably, λ 70/ λ 5Can reach 39/36.Glass in this compositing range also has specific refractory power (nd) between 1.89～1.91 and Abbe number (υ d) 30～32 with interior optics glass.
About common optical glass having high refractive index of the present invention and low transition temperature optical glass having high refractive index, each composition be limited in the above-mentioned compositing range the reasons are as follows described.
B 2O 3Be the main component that glass generates body, can keep the stability of glass, and be to introduce to improve refractive index composition La 2O 3, Nb 2O 5And TiO 2Important composition, but its quantity not sufficient 15%, tendency towards devitrification is increased sharply, it is very unstable that glass becomes, and just is difficult to obtain target nd value and surpass 30%.This composition 18～22% with interior best results.
SiO 2Also be that glass generates body, the proper viscosity when a spot of interpolation can be kept the chemical stability of glass and improve moulding, but can make glass melting become very difficult above 5% words, and produce not liquefactent, be difficult to obtain homogeneous glass.This composition 0.5～2.5% with interior best results.
The CaO composition can reduce the proportion of glass, and can improve chemical stability, this composition 0～6% with interior best results.If surpassing 6%, the introducing amount will be difficult to reach high index (nd) value.
Gd 2O 3Composition substitutes La 2O 3Very effective to the tendency towards devitrification that reduces glass, also can use Y 2O 3Or Yb 2O 3Composition substitutes La 2O 3Improve the devitrification of glass performance, reach the best consumption of this effect more than 1%, simultaneously in order not make devitrification of glass performance depreciation, Gd 2O 3Become deal to be controlled at below 10% and be advisable Y 2O 3Or Yb 2O 3Becoming deal to be controlled at below 6% is advisable.
La 2O 3Composition can make the low chromatic dispersion of the high refraction of glass, and by making itself and Gd 2O 3Coexistence can improve well crystallization property, so be main composition in the present invention, its quantity not sufficient 20% just makes glass form difficult, amount surpasses the optical constant that words 40% or more then are difficult to realize hope, and and Gd 2O 3The coexistence effect degenerate, can make on the contrary devitrification of glass tendency become big, obtain the good and stable glass of crystallization property, content preferably fixes in 22～37% scopes.
Ta 2O 5Composition can improve refractive index and chemical stability, and this component content all can form glass in 0～20% scope, but in order to save cost, its amount is just passable in 1～4% scope.In the glass of this invention, Ta 2O 5The glass that content is low compares Ta 2O 5The devitrification of glass performance that content is high is good, and glass is more stable.
In order to keep the objective optics constant, and for preventing devitrification of glass, WO 3Composition must be more than 1%, but surpasses 10%, and the degree of staining of glass will increase, and crystallization property also will degenerate.In low transition temperature optical glass having high refractive index, if WO 3Content surpasses 5%, causes easily the molded piece surface line to occur bursting in the compression molding process, and bigger to the corrosion function of mould, so WO 3Suitable content should be below 5%, so WO 3The optimum range of component content is 1～5%.
TiO 2Can improve specific refractory power and reduce specific gravity of glass, its quantity not sufficient 1% can't produce these effects, and surpasses 10%, and the crystallization property of glass and degree of staining will degenerate, and υ d will diminish than target value.Be reduction glass degree of staining, TiO in this invention 2Content is controlled at 5% and is advisable with interior.
The ZnO composition can reduce the transition temperature (T of glass effectively g), and be main component, make the glass of this invention be suitable for compression molding.And by making itself and WO 3The coexistence of composition, thereby and reduce glass transformation temperature effectively, prevent crystallization, its quantity not sufficient 1% can't realize its effect, but surpasses 25% optical constant that will be difficult to reach hope.In low transition temperature optical glass having high refractive index, be the transition temperature (T that reaches remarkable reduction glass g) purpose, it is especially obvious that its amount is controlled at 8～25% above-mentioned effects when above.
Nb 2O 5Composition can be kept desired high index of refraction, improves chemical stability, realize that these effects must be more than 10%, and if above 30%, Nb will occur 2O 5Not liquefactent, can reduce the homogenieity of glass and increase tendency towards devitrification, obtain uniformly, meltability and the good glass of crystallization property, preferably its amount is decided to be less than 25%.Make the especially outstanding glass of uniformity and crystallization property, preferably its amount is decided to be below 20%.
Li 2The O composition can reduce the transition temperature (T of glass effectively g), with Na 2O and K 2O compares, Li 2O reduces the transition temperature (T of glass g) effect the most remarkable, and the reduction glass refraction value of not too large amplitude.Also can effectively improve the dissolubility of glass, but Li 2If the amount of O composition surpasses 3% respectively, glass will become and be easy to crystallization.The optimum range of this composition is 0～2% in two kinds of glass of the present invention.Li 2The O composition is important composition in low transition temperature optical glass having high refractive index.
Al 2O 3Composition can improve viscosity when glass melting, prevent tendency towards devitrification and phase-splitting, instead can make the easier crystallization of glass but surpass 3%.
ZrO 2Composition can improve glass viscosity, reduces tendency towards devitrification, improves chemical stability, improves nd.In order to obtain positive effect, content should be advisable more than 3%, instead can increase tendency towards devitrification, the glass melting difficult but surpass 10%.Sb 2O 5Can be used as defrother and add arbitrarily, but 0.5% with interior just enough, special Sb 2O 5To become very big if surpass 0.5% degree of staining.And do not contain Sb 2O 5Composition is favourable to reducing degree of staining.Therefore its amount is controlled at below 0.5% or does not contain and is advisable.
Embodiment
The invention provides the prescription comparative example of 5 embodiment and existing 3 glass of high refractive index.Embodiment 1 to embodiment 5, comparative example a are to glass ingredient (weight percent), the optical constant specific refractory power (n of comparative example c d), abbe number (v d), transition temperature (T g), degree of staining (λ 70/ λ 5) and the recrystallization temperature upper limit (L T) list in the table 1.
So-called crystallization test is that the frit 500g that will sneak out puts into 300cc platinum crucible, difficulty according to the fusion of each test portion, with electric furnace 1200～1300 ℃ of meltings 3 hours, make glass even through stirring de-bubble in its fusion process, cooling then, again with each test portion with taking out after 1 hour every the insulation of 10 ℃ of temperature in 1150 ℃～1040 ℃ scopes, have or not crystallization with microscopic examination at last, determine recrystallization temperature.
As seen in Table 1, comparative example a to the glass of comparative example c at 1090 ℃ and following whole crystallization.Illustrate that these devitrification of glass tendencies are bigger, less stable.Relative therewith, the glass of 5 embodiment of the present invention has all reached the objective optics constant, has high refractive index and low transition temperature, with the glassy phase crystallization property more outstanding than having that compares Formulation Example.
Wherein, embodiment 1 to embodiment 3 is a glass in the common optical glass having high refractive index compositing range, and embodiment 4 and embodiment 5 are glass in the low transition temperature optical glass having high refractive index compositing range.
In addition, the glass of the above embodiment of the present invention 1 to embodiment 5 all can be by dropping into the platinum crucible with opticglass raw materials commonly used such as oxide compound, carbonate and nitrate after in the ratio weighing of reserving,, de-bubble, stir and make glass with 1200～1300 ℃ temperature melting 4～5 hours by the fusion characteristic of prescription evenly after the annealing sampling and testing obtains data.What need particularly point out is that the glass of the embodiment of the invention 1 to embodiment 5 is controlled by the atmosphere in fusion process and reduced degree of staining.
Table 1
Figure A20071005121600071
Figure A20071005121600081
The effect of invention: as mentioned above, because first kind optics glass of the present invention is the SiO of specific composition scope 2-B 2O 3-La 2O 3-ZnO-Nb 2O 5-TiO 2-WO 3-ZrO 2Be glass, have refractive index (nd) between 1.89～1.91 and Abbe number (υ d) 30～32 with interior optical constant, so have high index of refraction.Equations of The Second Kind optics glass of the present invention is the SiO of specific composition scope 2-B 2O 3-La 2O 3-ZnO-Nb 2O 5-TiO 2-WO 3-ZrO 2-Gd 2O 3(or Y 2O 3)-Li 2O is glass, has equally refractive index (nd) between 1.89～1.91 and Abbe number (υ d) 30～32 with interior optical constant, so have high index of refraction and have lower transition temperature (T g), be suitable for compression molding.This two classes glass coloring degree is little, objectionable constituent such as thoriated, lead, arsenic not, and chemical stability is good, and crystallization property and good uniformity, is suitable for producing in batches, can be used as glass of high refractive index that optics uses and widespread use.

Claims (2)

1. optical glass having high refractive index, it is characterized in that: its compositional range contains by oxide weight percentage: SiO 20～5%, B 2O 315～30%, Al 2O 30～3%, La 2O 320～40%, Y 2O 30～6%, Gd 2O 30～10%, Yb 2O 30～6%, TiO 21～10%, ZrO 23～10%, Nb 2O 510～30%, Ta 2O 30～20%, WO 31～10%, ZnO 1～25%, CaO 0～6%, Li 2O0～3%, Sb 2O 30～0.5%.
2. according to the described a kind of optical glass having high refractive index of claim 1, it is characterized in that: described compositional range by oxide weight percentage is: SiO 20～5%, B 2O 315～30%, Al 2O 30～3%, La 2O 320～40%, Y 2O 30～6%, Gd 2O 30～10%, Yb 2O 30～6%, TiO 21～10%, ZrO 23～10%, Nb 2O 510～30%, Ta 2O 30～20%, WO 31～5%, ZnO 8～25%, CaO 0～6%, Li 2O 0～3%, Sb 2O 30～0.5%.
CNA2007100512160A 2007-01-06 2007-01-06 Optical glass with high refractive index Pending CN101215082A (en)

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CN111018342B (en) * 2019-12-24 2022-04-15 成都光明光电股份有限公司 Optical glass, glass preform, optical element and optical instrument
US11802073B2 (en) 2020-09-10 2023-10-31 Corning Incorporated Silicoborate and borosilicate glasses with high refractive index and low density
US11976004B2 (en) 2020-09-10 2024-05-07 Corning Incorporated Silicoborate and borosilicate glasses having high refractive index and high transmittance to blue light
CN112142321A (en) * 2020-09-28 2020-12-29 成都光明光电股份有限公司 Optical glass, optical element and optical instrument
CN112159098A (en) * 2020-09-29 2021-01-01 成都光明光电股份有限公司 Optical glass, optical element and optical instrument
EP4059901A1 (en) 2021-03-19 2022-09-21 Corning Incorporated High-index borate glasses
WO2022197495A1 (en) 2021-03-19 2022-09-22 Corning Incorporated High-index borate glasses
NL2028260B1 (en) 2021-03-19 2022-09-29 Corning Inc High-Index Borate Glasses
US11999651B2 (en) 2021-08-10 2024-06-04 Corning Incorporated Silicoborate and borosilicate glasses having high refractive index and low density

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