CN103241942A - High-refraction and low-dispersion optical glass and manufacturing method - Google Patents
High-refraction and low-dispersion optical glass and manufacturing method Download PDFInfo
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- CN103241942A CN103241942A CN2013101991933A CN201310199193A CN103241942A CN 103241942 A CN103241942 A CN 103241942A CN 2013101991933 A CN2013101991933 A CN 2013101991933A CN 201310199193 A CN201310199193 A CN 201310199193A CN 103241942 A CN103241942 A CN 103241942A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000006185 dispersion Substances 0.000 title abstract description 22
- 239000005304 optical glass Substances 0.000 title abstract description 8
- 239000011521 glass Substances 0.000 claims abstract description 99
- 230000003287 optical effect Effects 0.000 claims abstract description 45
- 239000004615 ingredient Substances 0.000 claims abstract description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 238000007731 hot pressing Methods 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 4
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052681 coesite Inorganic materials 0.000 abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 3
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 abstract description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 abstract description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract description 2
- 238000002834 transmittance Methods 0.000 abstract description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 abstract 2
- 229910003069 TeO2 Inorganic materials 0.000 abstract 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 abstract 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 abstract 1
- 238000004031 devitrification Methods 0.000 description 23
- 238000004040 coloring Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000013461 design Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 4
- 230000010748 Photoabsorption Effects 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910003443 lutetium oxide Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012634 optical imaging Methods 0.000 description 1
- 239000005365 phosphate glass Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- XHGGEBRKUWZHEK-UHFFFAOYSA-L tellurate Chemical class [O-][Te]([O-])(=O)=O XHGGEBRKUWZHEK-UHFFFAOYSA-L 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
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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 relates to high-refraction and low-dispersion optical glass containing no GeO2 or TeO2 ingredient and a manufacturing method of the optical glass. The optical glass is characterized by comprising at least one of CaO, SrO and BaO, 1-10% of SiO2 and 5-18% of B2O3 counted by weight percent of oxides, wherein the content of SiO2 and B2O3 is smaller than 20%, the optical glass contains 20-30% of Gd2O3, 12-35% of La2O3, 0-8% of Y2O3, 5-20% of Ta2O5, 5-32% of Nb2O5, 0-8% of TiO2, larger than 0 while smaller than 7% of ZrO2, lager than 0 while smaller than 6% of ZnO, 0-5% of WO3, 0-8% of BaO, 0-4% of CaO, 0-4% of SrO, 0-2% of SnO2, 0-2% of Li2O, 0-1% of Sb2O3, the total content of Gd2O3, La2O3 and Y2O3 is smaller than 58%, and the total content of Ta2O5 and Nb2O5 is 17-38%. The refractive index (nd) of the glass is larger than 1.94, the abbe number (Vd) is an optical constant larger than 29 and smaller than 33, the upper limit of the internal transmittance (lambda t) of the glass is 405nm or lower, and the liquidus temperature is lower than 1210 DEG C.
Description
Technical field
The present invention relates to the opticglass of a kind of high refraction, low chromatic dispersion, and the method for making this opticglass.More specifically, the invention provides a kind ofly have specific refractory power more than 1.94, Abbe number (vd) is more than 29 but the optical constant of less than 33, and has high seeing through and the opticglass of good stability.Blank material by this opticglass can be used for secondary hot pressing and makes the not optical element of isomorph.
Background technology
In recent years, along with popularizing fast of slr camera, pick up camera, as the optical system in the slr camera, especially as the optical focal distance setting system of this class camera and pick up camera, also be widely used.Glass as the employed high refractive index of its optical system, low chromatic dispersion, it not only need satisfy the Design for optical system requirement of high performance slr camera, pick up camera and digital camera, more need satisfy the varifocal optical system of slr camera, pick up camera and to the demand of large size lens and the high requirement that sees through.Therefore, the opticglass of exploitation with extra-high-speed specific refractory power, low chromatic dispersion is very useful for the Design for optical system of slr camera.
As the opticglass in this class extra-high-speed specific refractory power field, at present known only is specific refractory power (nd) more than 1.94 or reach 2.00, as: series of phosphate glass, tellurate series or the high glass of Bi2O3 component content.And this class glass does not all reach low chromatic dispersion and high Abbe number, and has also that glass coloring is heavy, transmitance is low, many defectives such as vitrifying stability difference.As patent documentation: CN1010441553A, CN101279816A etc.
What also have introduces a large amount of expensive GeO2 compositions for the stability of keeping glass when increasing substantially specific refractory power, and as patent documentation: CN1955128A, and expensive can not the realization quantizes to produce.
Patent documentation: CN101289276A, CN101012103A for another example, its specific refractory power (nd) also reaches more than 1.94, but Abbe number (vd) less than 29, only with the comparison of identical specific refractory power, Abbe number (vd) is also less than the optical constant of the scope of the invention, can not satisfy that present novel list is anti-, varifocal optical system and the requirement of digital camera Design for optical system of pick up camera.
Moreover for this class extra-high-speed refractive index glass, along with the increase of specific refractory power, the painted of glass also will be deepened thereupon, and transmitance also will descend.Particularly, when the glass that uses painted tendency to deepen, the primary colours short wavelength side blue light susceptibility in the optical imaging system of its camera descends, and this will badly influence the sharpness of image quality, especially the image quality of the varifocal optical system of pick up camera.
Moreover, for the opticglass of the high refraction of this class, low chromatic dispersion, in the secondary hot pressing process, its good anti-increased devitrification resistance be realize repeatedly, secondary hot pressing repeatedly and do not occur the key of mist spot and devitrification phenomenon on die mould blank surface.
Moreover be top-priority from improving stability and the low cost operation that glass sees through and make, more than the defective of Cun Zaiing also is apparent.
Summary of the invention
The present invention carries out with deficiency and the defective of eliminating this high refracting glass existence for achieving the above object, its purpose is to provide a kind of specific refractory power (nd) more than 1.94, high dioptrics glass in Abbe number (vd) 29～33 scopes, have the viscosity of the moulding of being easy to, demonstrate good reproducibility simultaneously, and can be for the usefulness of secondary hot pressing moulding.
Another object of the present invention provide a kind of high permeability and cheaply, stable manufacture method.
The objective of the invention is to, be not only provide have above-mentioned scope, and can satisfy the optical constant of the optical system design requirements of camera, on the basis of not introducing expensive composition, realize stable quantification production and reach good secondary hot pressing and reproducibility thereof with low cost.
Moreover, another object of the present invention is to realize that optical lens has high seeing through, and maximum satisfies the zoom system, pancreatic system of slr camera, pick up camera and the high pixel design requirements of digital camera optical system.
The present invention is for reaching above-mentioned requirements, in constantly studying repeatedly, finding, can pass through SiO2, B2O3 content with and the adjustment of ratio, simultaneously to Gd2O3, La2O3, Ta2O5, Nb2O5, ZrO2, the optimization proportioning of essential component such as ZnO and to TiO2, BaO, WO3, CaO, SrO, Li2O, introducing and optimization proportioning etc. optional components, and do not introducing expensive GeO2 composition and Lu2O3, during rare earth compositions such as Yb2O3, not only reach the optical constant with above-mentioned scope, and also realized high seeing through, and can maximum amplitude satisfy secondary hot pressing, elimination is the optical element surface that comes across " mist spot " in hot pressing repeatedly.Finished the present invention for this reason.
Result of the present invention also finds, when the ratio of Ta2O5/Nb2O5 content was increased gradually, stability, glass and anti-increased devitrification resistance further improved, and have further finished the present invention.
More specifically, be used for realizing that the present invention is as described below:
(1) a kind of opticglass, specific refractory power (nd) is more than 1.94, and Abbe number (vd) is more than 29 but less than 33.When representing with weight %, described opticglass includes:
1～10% SiO
2
3～18% B
2O
3Wherein: (SiO
2+ B
2O
3)≤20%
20～30% Gd
2O
3
12～35% La
2O
3
0～8% Y
2O
3Wherein: (Gd
2O
3+ La
2O
3+ Y
2O
3)＜58%
5～20% Ta
2O
5
5～32% Nb
2O
5Wherein: (Ta
2O
5+ Nb
2O
5)=17～38%
0～8% TiO
2
Greater than 0 but less than 7% ZrO
2
Greater than 0 but less than 6% ZnO
0～5% WO
3
0～8% BaO
0～4% CaO
0～4% SrO
0～2% SnO
2
0～2% Li
2O
0～1% Sb
2O
3
Preferably, it contains following ingredients by weight percent:
1～8% SiO
2
6～16% B
2O
3Wherein: (SiO
2+ B
2O
3)≤18%
20～28% Gd
2O
3
14～33% La
2O
3
0～4% Y
2O
3Wherein: (Gd
2O
3+ La
2O
3+ Y
2O
3)＜55%
6～18% Ta
2O
5
7～28% Nb
2O
5Wherein: (Ta
2O
5+ Nb
2O
5)=19～36%
0～8% TiO
2
1～5% ZrO
2
1～4% ZnO
0～2% WO
3
0～7% BaO
0～2% CaO
0～1% SrO
0～0.5% SnO
2
0～2%Li
2O
0～0.1% Sb
2O
3
Preferably, described Gd
2O
3Content greater than 20%.
Preferably, Ta
2O
5With Nb
2O
5Total content less than 36%.
The specific refractory power of described opticglass is greater than 1.94, and Abbe number is 29～33.
The inside of described glass sees through (λ τ) upper limit less than 405nm; The density of described glass is less than 5.10g/cm
3
The transition temperature of described glass (Tg) is lower than 710 ℃, and liquidus temperature (LT) is not higher than 1210 ℃.
The present invention also provides a kind of optical element, and it is prepared from by aforesaid opticglass.
The present invention also provides a kind of manufacture method of optical element, may further comprise the steps: admixtion or be melted into uniform glass liquid state to grog preparation, reheat, leak materials device via platinum and flow into cooling in the specific forming mould, be cured as constant thickness and width, make the blank material that aforementioned opticglass forms.
Further, aforementioned blank material is cut, is processed into required specification and weight, pass through the softening furnace thermoplastic again, and under soft state, it is pressed, obtain the not optical element of the secondary hot pressing of isomorph.
Optical glass refractive index of the present invention (nd) is more than 1.94, and Abbe number (vd) is 29～33, sees through in the glass to be lower than 405, and density is lower than 5.10, and transition temperature (Tg) is lower than 710 ℃, and is best in quality.In addition, with existing high dioptrics glassy phase ratio, not only have the characteristic of high refractive index and low chromatic dispersion, and also have good anti-increased devitrification resistance and low cost, can under stable status, realize low cost operation and volume production.
Obviously, according to foregoing of the present invention, according to ordinary skill knowledge and the customary means of this area, not breaking away under the above-mentioned basic fundamental thought of the present invention prerequisite, can also make modification, replacement or the change of other various ways.
The embodiment of form is described in further detail foregoing of the present invention again by the following examples.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.All technology that realizes based on foregoing of the present invention all belong to scope of the present invention.
Embodiment
It is more than 1.94 that opticglass of the present invention has specific refractory power (nd), Abbe number (vd) is more than 29 but less than 33, and the characteristics with high permeability, and when being directly formed to the blank material with the glass liquid state, have satisfactory stability and a reproducibility, in the secondary hot pressing process, through secondary hot pressing repeatedly and devitrification do not occur, and make the optical element of all kinds of specifications.
Below will describe the glass ingredient and each component concentration and each per-cent of organizing total content that constitute the included glass 1～11 of opticglass of the present invention in detail, represent with weight % respectively.
For realizing above-mentioned every performance, opticglass of the present invention comprises the SiO as the component that forms glass network
2And B
2O
3, comprise as the Gd that improves specific refractory power
2O
3, La
2O
3, Ta
2O
5, Nb
2O
5And TiO
2Etc. component, wherein the introducing amount of alkaline earth metal oxide CaO, SrO, BaO is at least a or two, limits SnO simultaneously
2, Li
2The introducing amount of O.
In the glass of high refraction of the present invention, low chromatic dispersion, SiO
2Be as forming the essential component of glass network, still the most effective expansion glass formation range, strengthen the component of anti-increased devitrification resistance.Work as SiO
2The introducing amount cross when low, the stable extreme difference of glass, and glass coloring is increased the weight of is difficult to form high-quality glass.If introducing is measured when excessive, the solubility variation of fusing, optical constant reduce, and are difficult to obtain desirable specific refractory power and dispersion values.Therefore preferred 1～10%, more preferably 1～8%, further preferred 2～7%.
B
2O
3Be to be most effective to form the glass network composition, and can be effective to the component that reduces solubility and reduce temperature of fusion.But in glass of the present invention, as excessive introducing, specific refractory power is reduced, glass coloring also will be deepened simultaneously.Therefore, the introducing amount is controlled 3～18%, and preferred 6～16%, further preferred 6～15%.
Purpose of the present invention not only will realize the specific refractory power of extra-high-speed, must have good anti-increased devitrification resistance and stability simultaneously.But, work as SiO
2+ B2O
3Total content did not then reach desired optical constant greater than 20% o'clock.Therefore with above-mentioned total content control in 20%, more preferably 18% or lower.
Gd as rare earth composition
2O
3Have and La
2O
3The oxide compound of same function all is to have the component that improves high refractive index, moreover, also has and improves that visible region sees through and the effect of stability, glass.But when excessive introducing, stability, glass then will reduce, and the glass increased devitrification resistance will be worsened.Therefore, Gd
2O
3Introducing amount control 20～30%, more preferably 20～28%, further preferred 20～27%.
La
2O
3Be the essential component that obtains high refraction, low chromatic dispersion, yet work as La
2O
3The introducing amount will be difficult to reach desired optical constant less than 10% o'clock, and when greater than 40% the time, the anti-devitrification of glass descends, and therefore can not obtain the glass of any stable manufacturing.Therefore, La
2O
3Introducing amount control 10～40%, preferred 12～35%, more preferably 14～33%.
Y as similar rare earth oxide
2O
3Have and La
2O
3Any adding component of same function, yet---as excessive introducing, the stability of glass will descend, and glass transformation temperature will be risen.Therefore, its introducing amount is controlled 0～8%, and preferred 0～4% or lower.
In addition, the rare earth oxide that contains single component with this glass is compared, and glass ingredient contains multiple rare earth oxide (Gd simultaneously
2O
3+ La
2O
3+ Y
2O
3) then can obviously improve stability, glass, and increase the total content of rare earth oxide.Particularly in glass of the present invention, has the Gd that improves specific refractory power as containing simultaneously
2O
3, La
2O
3, Y
2O
3Etc. component, then can effectively, significantly improve specific refractory power and stability, glass, surpass 60% as total amount, the anti-increased devitrification resistance of glass will worsen.Therefore, (Gd
2O
3+ La
2O
3+ Y
2O
3) overall control is below 60%, and is preferred 45～58%, more preferably 48～55%.
Ta
2O
5Be to have to increase substantially stability, glass and raisingization stability and adjustment optical constant and make optical constant reach the important component of setting range.But too much as the introducing amount, stability, glass is with variation, and dispersion values also will increase, and the introducing amount is very few, is difficult to play the effect of stability again.Therefore, its introducing amount is controlled to be 5～20%, and is preferred 5～19%, and more preferably 6～18%.
In glass of the present invention, Nb
2O
5Be the important component that significantly improves specific refractory power and dispersion values, and can significantly improve the anti-increased devitrification resistance of glass and improve stability, glass.But, when its introducing amount is lower than 5%, then be difficult to obtain above-mentioned effect, as greater than 35% o'clock, then occur on the contrary, anti-increased devitrification resistance and the stability of glass all will descend, and Abbe number also will exceed setting range.Therefore, its preferable range is 5～32%, and more preferably scope is 5～30%, and further preferable range is 7～28%.
For satisfying above-mentioned optical constant and realize high seeing through, preferred Ta
2O
5+ Nb
2O
5Total content control below 38%, more preferably Ta
2O
5+ Nb
2O
5Total introducing amount be 36% or lower.
In glass of the present invention, TiO
2It is the component with the specific refractory power of significantly improving and dispersion values.Yet, when the introducing amount is too much, not only will increase the glass dispersion values, also will aggravate the absorption to short wavelength side section and long-wave band simultaneously, glass coloring is increased the weight of, simultaneously the anti-increased devitrification resistance of glass and solubility variation.Consider from preferential reduction glass coloring and dispersion values aspect, preferably with TiO
2The introducing amount be controlled to be 0～8.0%, more preferably be controlled to be 0～7.5%, more preferably 0～7.0%..
ZrO
2It is the component that improves stability, glass and anti-increased devitrification resistance and adjust optical constant.A spot of introducing then has the effect that improves stability, glass, and as excessive introducing, not only stability, glass will descend, and dispersion values also will increase, and the solubility of glass is also with variation simultaneously.Therefore, its introducing amount is greater than 0 but less than 7%, and is preferred 0.5～6%, and more preferably 1～5%.
In the present invention, ZnO is the component that reduces transition temperature, improves solubility and raising stability, glass.Yet its content is difficult to reach specific refractory power and the dispersion values of expection too much, and glass coloring also will be deepened.Therefore, for making glass reach desired optical constant and alleviate glass coloring, its introducing amount control is greater than 0 but less than 6%, and is preferred 0.5～5%, and more preferably 1～4%.
WO
3It is the component that strengthens anti-increased devitrification resistance, improves stability, glass and specific refractory power.In glass of the present invention, as excessive introducing, will cause dispersion values to increase, the photoabsorption of visible region short wavelength side will strengthen, and the glass coloring tendency increases the weight of.Therefore its introducing amount is controlled to be 0～5%, and is preferred 0～3%, and more preferably 0～2% or lower.
Opticglass of the present invention contains at least a as glass ingredient among CaO, SrO and the BaO, and it introduces total amount less than 15%.
CaO and SrO have the transmitance that improves visible region short wavelength side section, and improve anti-increased devitrification resistance and accelerate the glass metal clarification.But, when two kinds introducing amounts surpass 8%, can reduce not only that glass refraction, glass viscosity diminish, anti-increased devitrification resistance worsens.Therefore, its introducing amount of two kinds is 0～8%, and is preferred 0～6%, more preferably 0～4%, further preferred 0～3% or lower.
BaO not only has the raising specific refractory power and also has the effect that raising glass visible region short wavelength side sees through, and also has the effect that improves stability, glass and anti-devitrification.But when its introducing amount surpassed 10%, not only glass refraction can reduce, and glass increased devitrification resistance deterioration simultaneously, stability descend thereupon.Therefore, introducing amount-control is 0～8%, and is preferred 0～7%, and further preferred 0～6.5%.
Li
2Viscosity when O helps to improve melting properties, reduces temperature of fusion, improves frit and increases moulding.But, surpass 2% as the introducing amount, will make the anti-increased devitrification resistance control breakdown of glass, specific refractory power also will decline to a great extent simultaneously.Therefore, its introducing amount is 0～2%, and is preferred 0～1.0%, more preferably 0～0.5% or lower.
SnO
2Have and ZrO
2Identical effect, still, when the introducing amount was too much, the glass meltability was with variation, and specific refractory power and dispersion values also will reduce, and glass transformation temperature (Tg) will fast rise.Thereby its introducing amount is preferred 0～2.0%, more preferably 0～1.0% or lower.
Sb
2O
3Be any additive that uses as finings, by the adding of trace, can alleviate the photoabsorption that the reduction owing to Fe impurity causes, and alleviate glass coloring.As excessive interpolation, will play opposite effect, also will make glass inner quality variation.Therefore, preferably the amount of being introduced into is controlled to be 0～1%, and is preferred 0～0.2%, and more preferably 0～0.1% or lower.
As mentioned above, in order to be not only the performance that realizes high refraction, low chromatic dispersion, more to reach the photoabsorption that reduces the visible light short wavelength side simultaneously, and improve the stability that glass is made.Preferred restriction SiO
2, B
2O
3, Gd
2O
3, La
2O
3, Ta
2O
5, Nb
2O
5, TiO
2, BaO, ZrO
2, ZnO etc. component introducing amount be 97% or more, WO
3, CaO, SrO, SnO
2, Li
2The introducing amount of components such as O is 3% or still less, its total introducing amount is 100%.
Can realize higher specific refractory power and not contain expensive GeO at opticglass of the present invention
2, TeO
2, Lu
2O
3, Yb
2O
3Deng oxide compound.
Consider economy and low-cost volume production, and do not introduce GeO
2, Lu
2O
3, Yb
2O
3Deng oxide compound, and can realize stable volume production.
Optical glass refractive index of the present invention (nd) is more than 1.94, and Abbe number (vd) is 29～33.When progressively heightening specific refractory power, the anti-increased devitrification resistance of glass easily descends or worsens, yet the present invention's opticglass of the present invention can be realized excellent anti-increased devitrification resistance and reach high transmitance, thereby can further improve specific refractory power (nd).Therefore, specific refractory power of the present invention (nd) preferably at least 1.94, more preferably 1.95 or 1.98.Stability for realizing making it is desirable to specific refractory power (nd) is limited in 2.00 or littler, more preferably is limited in 1.98 or littler.
Again and, for stability that realize to make with alleviate glass coloring, the Abbe number of opticglass of the present invention (vd) is preferably 29～33.
Opticglass of the present invention mainly is for obtaining optical element by the softening compacting of second-heating or through the cold working cutting, and through being processed into optical lens.
According to opticglass of the present invention, by constituent optimization and process corrections, interior see through (wavelength X τ 70) are controlled to below the 405nm preferred 400nm or littler.See through (wavelength X τ 5) control below 365nm, preferred 360nm or littler with interior.Because opticglass of the present invention has 70% or higher see through and (λ τ 5) more is offset the shortwave direction in (λ τ 70) wavelength region, thereby is suitable for the optical lens as various high pixels.
The prerequisite that realizes the stability of manufacturing is that glass has low liquidus temperature, and when the anti-increased devitrification resistance of glass descended, its liquidus temperature can sharply raise the stability, glass variation.Thereby the liquidus temperature of opticglass of the present invention is controlled below 1210 ℃, more preferably 1190 ℃ or lower.
The character of embodiment 1 opticglass of the present invention
Table 1,2 shown that the Bo Li Group of the embodiment № 1～№ 11 of opticglass of the present invention becomes and with the composition of the comparative example № a～№ c of glassy phase of the present invention high refracting glass of the same type.Below measuring in each embodiment and the comparative example is the opticglass that obtains by-4.0/h annealing rate and cooling, specific refractory power (nd), Abbe number (vd), the interior measurement result that sees through (λ τ 70) and (λ τ 5), density (ρ), transition temperature (Tg), liquidus temperature (LT), the result who measures provides in table 1,2.
With raw materials such as the corresponding various oxide compounds of the raw material of each component, carbonate and nitrate, carrying out weighing by the composition of each embodiment and comparative example after as calculated mixes, make admixtion, it is added in platinum container or the yellow platinum alloy container, after fusing under 800 ℃～1350 ℃ the temperature, stirring, clarification and homogenizing, pour into or leak the material pipe through platinum and bleed to become in the mould
Type is all size, makes opticglass of the present invention through annealing.
The annealing rate of temperature fall that every performance specific refractory power (nd) of measuring above-mentioned glass by the following method and Abbe number (vd) are measured with-4.0/h obtains glass specimen.
In see through (λ τ): measure 5mm, 10mm, the interior of 15mm sample with three parallel polished surfaces respectively and see through, namely to be defined as the wavelength (nm) at λ τ 70,5% places be λ τ 5 to the wavelength at 70% place (nm).(the interior transmittance that sees through when not comprising the specimen surface reflection loss)
Determine density (ρ): adopt Archimedes's method to measure.
Glass transformation temperature (Tg): adopt the thermal analyzer measurement device, temperature rise rate is to measure under 4.0 ℃/minute.
Liquidus temperature (LT): in 0.3L platinum container or yellow platinum container, add 500g glass, be set in the test smelting furnace at 10 ℃ of intervals, under differing temps, be incubated 2h respectively and obtain sample, whether there is crystallization to occur by microscopic examination, will confirms that the minimum temperature of no crystallization is as liquidus temperature (LT).
Table 1 fusing embodiment (weight %)
Table 2 fusing embodiment (weight %)
Shown in table 1,2, the opticglass № 1～№ 11 of the embodiment of the invention has the optical constant of above-mentioned scope, be that specific refractory power (nd) is 1.94065～2.00012, Abbe number (vd) 29.08～32.76, see through the upper limit in the glass less than 405nm, under be limited to 354nm, proportion is lower than 5.10, and its transition temperature (Tg) is below 710 ℃, and liquidus temperature (LT) is below 1210 ℃.Can not only realize stable volume production, also can realize the well reproduced of secondary hot pressing.
Otherwise shown in the comparative example in the table 2, though a example specific refractory power (nd) reaches more than 1.94, the Abbe number (vd) close with specific refractory power of the present invention then only is 25.89 relatively.Therefore, do not belong to optical constant of the present invention.
So same, though b example specific refractory power (nd) has also reached more than 1.94, Abbe number (vd) does not therefore belong to optical constant of the present invention less than 29 yet.Also contain expensive Lu simultaneously
2O
3Composition can not be realized low-cost volume production.
Above a example exists also with the b example that glass coloring is dark, transmitance is low, and the optical system that can not be used for novel slr camera, pick up camera designs.
C example specific refractory power (nd) also reaches more than 1.94, but Abbe number (vd) only is 23.6, differs greatly with optical constant of the present invention.Simultaneously owing to contain TeO
2, Bi
2O
3Composition, glass sees through rate variance, the requirement that the optical design of discontented unabridged version invention sees through height.
To sum up, it is 1.94 or bigger that opticglass of the present invention has high refractive index (nd), and Abbe number (vd) is 29～33, and has high permeability and excellent manufacturing stability, can be prepared into various optical elements, be applied in the optical system of slr camera, pick up camera, digital camera and mobile phone.
Claims (10)
1. opticglass, it is characterized in that: it contains following ingredients by weight percent:
1～10% SiO
2
3～18% B
2O
3Wherein: (SiO
2+ B
2O
3)≤20%
20～30% Gd
2O
3
12～35% La
2O
3
0～8% Y
2O
3Wherein: (Gd
2O
3+ La
2O
3+ Y
2O
3)＜58%
5～20% Ta
2O
5
5～32% Nb
2O
5Wherein: (Ta
2O
5+ Nb
2O
5)=17～38%
0～8% TiO
2
Greater than 0 but less than 7% ZrO
2
Greater than 0 but less than 6% ZnO
0～5% WO
3
0～8% BaO
0～4% CaO
0～4% SrO
0～2% SnO
2
0～2% Li
2O
0～1% Sb
2O
3
2. opticglass according to claim 1, it is characterized in that: it contains following ingredients by weight percent:
1～8% SiO
2
6～16% B
2O
3Wherein: (SiO
2+ B
2O
3)≤18%
20～28% Gd
2O
3
14～33% La
2O
3
0～4% Y
2O
3Wherein: (Gd
2O
3+ La
2O
3+ Y
2O
3)＜55%
6～18% Ta
2O
5
7～28% Nb
2O
5Wherein: (Ta
2O
5+ Nb
2O
5)=19～36%
0～8% TiO
2
1～5% ZrO
2
1～4% ZnO
0～2% WO
3
0～7% BaO
0～2% CaO
0～1% SrO
0～0.5% SnO
2
0～2%Li
2O
0～0.1% Sb
2O
3
3. opticglass according to claim 1 and 2 is characterized in that: described Gd
2O
3Content greater than 20%.
4. opticglass according to claim 1 and 2 is characterized in that: Ta
2O
5With Nb
2O
5Total content less than 36%.
5. according to any described opticglass of claim 1～4, it is characterized in that: the specific refractory power of described opticglass is greater than 1.94, and Abbe number is 29～33.
6. according to any described opticglass of claim 1～4, it is characterized in that: the inside of described glass sees through (λ τ) upper limit less than 405nm; The density of described glass is less than 5.10g/cm
3
7. according to any described high dioptrics glass of claim 1～4, it is characterized in that: the transition temperature of described glass (Tg) is lower than 710 ℃, and liquidus temperature (LT) is not higher than 1210 ℃.
8. optical element, it is characterized in that: it is prepared from by each described opticglass of claim 1-7.
9. the manufacture method of an optical element is characterized in that: may further comprise the steps:
Admixtion or be melted into uniform glass liquid state to grog preparation, reheat, leak materials device via platinum and flow into cooling in the specific forming mould, be cured as constant thickness and width, make the blank material that is formed by each described opticglass in claim 1 or 3.
10. manufacture method according to claim 9 is characterized in that:
Be with the cutting of the blank material of claim 9, be processed into required specification and weight, pass through the softening furnace thermoplastic again, and under soft state, it is pressed, obtain the not optical element of the secondary hot pressing of isomorph.
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| PCT/CN2013/090312 WO2014187132A1 (en) | 2013-05-24 | 2013-12-24 | High-refraction and low-dispersion optical glass and preparation method therefor |
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| CN103241942B CN103241942B (en) | 2016-01-13 |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN103241942B (en) | 2016-01-13 |
| WO2014187132A1 (en) | 2014-11-27 |
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Address after: West Port Avenue 610000 Sichuan city of Chengdu province Shuangliu County Southwest Airport Economic Development Zone No. 1499 two Patentee after: CHENGDU YOULITE PHOTOELECTRIC TECHNOLOGY CO., LTD. Address before: West Port Avenue 610225 Sichuan city of Chengdu province Shuangliu County Southwest Airport Economic Development Zone No. 1499 two Patentee before: Chengdu Unite Optoelectronics Technology Co., Ltd. |