CN102424523B - Optical glass, prefabricated member for mould pressing and optical element - Google Patents

Optical glass, prefabricated member for mould pressing and optical element Download PDF

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CN102424523B
CN102424523B CN201110265549.XA CN201110265549A CN102424523B CN 102424523 B CN102424523 B CN 102424523B CN 201110265549 A CN201110265549 A CN 201110265549A CN 102424523 B CN102424523 B CN 102424523B
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glass
opticglass
optical glass
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CN102424523A (en
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匡波
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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 PCT/CN2012/081039 priority patent/WO2013034081A1/en
Priority to JP2014528841A priority patent/JP5813233B2/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

Abstract

The invention provides optical glass with a refraction index being above 1.88 and an Abbe number being above 37. The optical glass has an excellent penetration rate and a low transition temperature and is suitable for precise mould pressing forming. The optical glass comprises the following materials in percentage by weight: more than 1% but less than 10% of SiO2, 10-20% of B2O3, 25-35% of La2O3, 10-20% of Gd2O3, more than 0 but less than 5% of Lu2O3,; 10-20% of Ta2O5, 8-15% of ZnO, 0.1-2% of LiO2, 0.5-8% of ZrO2, 5-15% of WO3, 0.1-3% of TiO2 and 0-0.2% of Sb2O3, wherein the value of La2O3/(La2O3+Gd2O3+Lu2O3) is less than 0.67. As high-refraction and low chromatic dispersion optical glass provided by the invention, the glass with high refraction rate and stable production can be obtained through adjusting the contents of the components of La2O3, Gd2O3 and Lu2O3, and therefore, the optical glass is suitable for precise mould pressing forming and can meet the imaging requirements of an optical system and equipment.

Description

Opticglass, prefabricated part for mold pressing and optical element
Technical field
The present invention relates to a kind of opticglass, prefabricated part for mold pressing and optical element, the prefabricated part for mold pressing that more particularly, the present invention relates to a kind of high-refraction low-dispersion optical glass for mold, is formed by described glass and the optical element being formed by described glass.
Background technology
High-refraction low-dispersion optical glass for mold is widely applied in optical design, and particularly specific refractory power is more than 1.88, and Abbe number is more than 37 opticglass.But opticglass transmittance and specific refractory power are closely related conventionally, the higher often transmitance of specific refractory power variation, the aggravation of glass coloring tendency.
In addition, when precise compression molding glass elements,, conventionally need under hot environment, carry out, often there is the problem such as oxidation, corrosion of the forming face of mold, be difficult to realize at low cost and produce in a large number.For this reason, the glass using in precision moulded formation should have low transition temperature (Tg) as far as possible, and compression molding has also proposed higher requirement to the chemical stability such as acidproof, water-fast of glass.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of specific refractory power more than 1.88, and Abbe number is more than 37 opticglass, this opticglass transmitance excellence, and transition temperature is low, is suitable for precision moulded formation.
The technical scheme that technical solution problem of the present invention adopts is: opticglass, its weight percent content is: be greater than 1% and be less than 10% SiO 2; The B of 10-20% 2o 3; The La of 25-35% 2o 3; The Gd of 10-20% 2o 3; Be greater than 0 and be less than 5% Lu 2o 3; Wherein, La 2o 3/ (La 2o 3+ Gd 2o 3+ Lu 2o 3) be less than 0.67; The Ta of 10-20% 2o 5; The ZnO of 8-15%; The LiO of 0.1-2% 2; The ZrO of 0.5-8% 2; The WO of 5-15% 3; The TiO of 0.1-3% 2; The Sb of 0-0.2% 2o 3.
Further, described SiO 2: 2-6%.
Further, described B 2o 3: 12-15%.
Further, described La 2o 3: 27-32%.
Further, described Gd 2o 3: 13-17%.
Further, described Lu 2o 3be greater than 0 and be less than 2%.
Further, described La 2o 3/ (La 2o 3+ Gd 2o 3+ Lu 2o 3) be less than 0.67 and be greater than 0.60.
Further, described ZnO:10-13%.
Further, described LiO 2: 0.2-1%.
Further, described ZrO 2: 1-6%.
Further, described WO 3: 8-13%.
The prefabricated part for mold pressing that adopts above-mentioned opticglass to form.
The optical element that adopts above-mentioned opticglass to form.
The invention has the beneficial effects as follows: the present invention is as a kind of high-refraction low-dispersion optical glass for mold, by adjusting La 2o 3, Gd 2o 3with Lu 2o 3composition content, can obtain high refractive index and produce stable glass; By controlling La 2o 3/ (La 2o 3+ Gd 2o 3+ Lu 2o 3) ratio, can obtain described optical constant and effectively improve the transmitance of described glass; The introducing of ZnO can reduce the transition temperature of glass, also can improve the chemical stability of glass; A small amount of introducing LiO2 also can effectively reduce the transition temperature of glass, and the present invention introduces WO3 in right amount, can improve the transmitance of described glass.Optical glass refractive index scope of the present invention reaches more than 1.88, and Abbe number scope is more than 37, glass transmitance excellence, λ 70below 385nm, glass transformation temperature, below 610 DEG C, is suitable for precise compression molding, and can meet the imaging demand of optical system and equipment.
Embodiment
To the technical scheme in the embodiment of the present invention be clearly and completely described below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Opticglass of the present invention contains SiO 2composition, SiO 2can improve the stability of glass, can also effectively regulate the liquid phase viscosity of glass, improve the crystallization property of glass; If SiO 2content too low, aforementioned DeGrain; SiO 2too high levels, glass melting variation, transition temperature raises.Therefore, SiO 2addition for being greater than 1% and be less than 10%, preferred content is less than 8% for being greater than 1%, more preferably content is 2%-6%.
As a kind of effective oxide that forms glass network structure, B 2o 3it is the necessary component that obtains the low dispersion opticglass of high refraction.B in the present invention 2o can effectively improve the meltbility of glass, reduces smelting temperature and viscous flow temperature.B 2o 3content is too much, does not reach the high refractive index of described glass, and content is too low, and glass is unstable; Therefore, require its content for being at least 10%, but work as B 2o 3when content is greater than 20%, specific refractory power declines, thereby cannot obtain the refractive index glass as the finished product of the present invention; Therefore its addition is 10-20%, and preferred content is 11-18%, and more preferably content is 12-15%.
La 2o 3it is the important component that obtains high-refractivity and low-dispersion glass, its content requirement is 25-35%, when its content is lower than 25% time, specific refractory power and low dispersivity all decline, in the time that it is greater than 35%, devitrification resistance declines, and therefore cannot stablize and prepare glass, preferred content is 27-32%, more preferably the scope of 28-32%.
Gd 2o 3composition also have improve glass specific refractory power, make the effect of its low dispersion, appropriate ratio ground uses Gd 2o 3, contribute to improve the devitrification resistance property of high refractive low dispersive glass.But if its amount is very few, above-mentioned effect is insufficient, particularly can not get described Abbe number index; If its amount too much, devitrification resistance variation on the contrary.Therefore, its content is 10-20%, and preferable range is 13-17%.
Lu 2o 3specific refractory power and the effective composition of increase Abbe number to improving glass equally., make the forthright deterioration of devitrification when too a large amount of containing sometimes, specific gravity of glass increases; Lu 2o 3also be a kind of expensive rare earth oxide, therefore selected its content is less than 5% for being greater than 0 simultaneously, and preferable range is less than 2% for being greater than 0.
Contriver is by research discovery with keen determination, by La in the present invention 2o 3, Gd 2o 3with Lu 2o 3when three kinds high refraction rare earth oxides are introduced in glass, can effectively increase the stabilizing dissolved degree of the low dispersion oxide compound of high refraction in glass simultaneously, especially, by adjusting their content ratio, make described La 2o 3/ (La 2o 3+ Gd 2o 3+ Lu 2o 3) scope meet be less than 0.67, preferable range is less than 0.67 and be greater than 0.60, can make glass reach specific refractory power (nd) more than 1.88, and Abbe number is controlled at more than 37 optical constants, and the light transmission excellence of glass, can realize stably manufactured in batches; Above-mentioned effect is to be greater than 0 Lu that is less than 2% having added scope especially 2o 3after more obvious.
Ta 2o 5be the component that obtains high refractive index, can obviously improve the devitrification resistance of glass simultaneously.To reduce the Abbe number of glass but addition is too high, it is also a kind of noble heavy metal oxide simultaneously, and usage quantity is defined as 10-20%, and preferred content is 10.5-15%.
ZnO can effectively reduce the transition temperature of glass in the present invention, also be the necessary component that forms high-refractivity and low-dispersion glass, can improve the anti-opacity of glass and reduce its viscous flow temperature, also have simultaneously and improve chemical durability of glass and the effect that suppresses crystallization, its addition should be more than 8%, otherwise described glass melting degradation, and chemical stability worsens; But its content should be below 15%, otherwise cannot obtain the low dispersion as the finished product of the present invention; Therefore, its content is 8-15%, and preferred content is 10-13%.
Li 2o contains on a small quantity can effectively reduce glass transformation temperature (Tg), improve the meltbility of glass, but usage quantity too much can reduce glass refraction, worsens stability, therefore its content 0.1-2%; Preferably 0.2-1%.
Add appropriate ZrO 2can play the anti-impervious effect of improvement glass, but also can effectively reduce the high temperature viscosity of described glass, improve chemical stability, ZrO 2addition be at least 0.5%, otherwise do not reach effect, but its content should be below 8%, otherwise the easy crystallization of glass; Therefore its content is 0.5-8%, and preferred content is 1-6%, and more preferably content is 2-5%.
WO 3composition has raising glass refraction, improves the effect of devitrification of glass, and appropriate introducing can make glass make moderate progress at the light transmittance in the short wavelength region of visible region, but in the present invention, if content is higher than 15%, transmitance on the contrary can variation, and devitrification of glass performance depreciation.Therefore, its content is 5-15%, and preferred content is 8-13%.
In the present invention, introduce a small amount of TiO 2substitute WO 3can make glass there is higher specific refractory power, lower proportion, but as itself and WO 3while coexisting, if content higher than 3%, glass transmitance can worsen; Therefore its content range is 0.1-3%, and preferable range is 0.5-2%.
Sb 2o 3deaeration when composition can be for glass melting, if but its content is too much, the transmissivity variation in the short wavelength region of visible region.Therefore, can preferably contain as the upper limit using 0.2%, more preferably 0.1%, most preferably 0.05%.
According to the present invention, described opticglass is preferably prepared according to following steps:
Taking oxide compound, oxyhydroxide, carbonate or the nitrate of above-mentioned each component as raw material, fully mix and be placed in platinum crucible, in 1200-1400 DEG C, preferably, after fusing at 1250-1350 DEG C, clarification, homogenizing, obtain melten glass;
After below described melten glass is down to 1100 DEG C, be poured in the metal pattern of preheating;
At 600 DEG C, the melten glass in described metal pattern is carried out to slow cooling annealing, thereby obtain opticglass.
Described opticglass is carried out to performance test, and method is as follows:
(υ d) is worth the annealing value for-30 DEG C/h, and specific refractory power and Abbe number are tested according to the specific refractory power to colouless optical glass providing in " GB/T 7962.1-1987 " and the testing method of abbe number for specific refractory power (nd) and Abbe number;
Glass is made into the sample of 10mm ± 0.1mm thickness, tested glass reaches the wavelength X of 70% correspondence in transmittance 70.
Transition temperature (Tg) is tested according to " GB/T7962.16-1987 colouless optical glass testing method linear expansivity, transition temperature and sag temperature ", that is: sample is in certain temperature range, 1 DEG C of the every rising of temperature, on the expansion curve of sample, low-temperature region and the extension of high-temperature area straight line portion are intersected to the corresponding temperature of its intersection point.
Through test, opticglass provided by the invention has following performance: ranges of indices of refraction is more than 1.88; Abbe number is more than 37; Corresponding wavelength X when transmittance reaches 70% 70below 385nm; Transition temperature is below 610 DEG C.
Opticglass provided by the invention has the optical constant of high-refractivity and low-dispersion, excellent transmitance and low transition temperature.The specific refractory power of opticglass provided by the invention is more than 1.88, and preferable range is 1.88-1.90; Abbe number is more than 37, preferably 37-40, more preferably 37-38; Corresponding wavelength X when transmittance reaches 70% 70below 385nm; Transition temperature reaches below 610 DEG C, preferably below 605 DEG C, more preferably below 602 DEG C.
Opticglass of the present invention can be used as pressure forming glass preshaping body material, or also can be directly by melten glass pressure forming.Manufacture method and thermoforming process during as glass preshaping body are not particularly limited, and can use known manufacture method and forming method.
In addition, the glass preshaping body that also can make opticglass of the present invention carry out press working, manufactures optical element, or also can adopt directly and melting, softening opticglass are carried out to press working, manufacture optical element.
In addition, optical element can be used as the such as various lens such as biconvex, concave-concave, plano-convex, plano-concave, meniscus, speculum, prism, diffraction grating etc.
Below, describe for embodiments of the invention, but the present invention is not subject to the restriction of these embodiment.
According to following steps, make opticglass according to the composition and ratio shown in table 1-2:
Table 1-2 has provided embodiment glass composition.Respectively with raw material forms such as the corresponding oxide compound of each component, carbonate, nitrate, oxyhydroxide, become shown in table 1-2 and form and weigh respectively after its vitrifying according to making, fully mix and be placed in platinum crucible, after fusing at 1250-1350 DEG C, clarification, homogenizing, obtain melten glass;
After below described melten glass is down to 1100 DEG C, be poured in the metal pattern of preheating;
At 600 DEG C, the melten glass in described metal pattern is annealed, obtain opticglass.
Described opticglass is carried out to performance test, and result is referring to table 1-2, and table 1-2 is the performance perameter of the opticglass prepared of the embodiment of the present invention.
The proportioning raw materials of opticglass prepared by table 1: embodiment of the present invention 1-5
Figure BDA0000090014460000051
Figure BDA0000090014460000061
The proportioning raw materials of opticglass prepared by table 2: embodiment of the present invention 6-10
Figure BDA0000090014460000062
From table 1-2, opticglass provided by the invention has high refractive index, the transmitance performance of excellence and good chemical stability.

Claims (14)

1. opticglass, is characterized in that, its weight percent content is: be greater than 1% and be less than 10% SiO 2; The B of 10-20% 2o 3; The La of 25-35% 2o 3; The Gd of 10-20% 2o 3; Be greater than 0 and be less than 5% Lu 2o 3; Wherein, La 2o 3/ (La 2o 3+ Gd 2o 3+ Lu 2o 3) below 0.65; The Ta of 10-20% 2o 5; The ZnO of 8-15%; The Li of 0.1-2% 2o; The ZrO of 0.5-8% 2; The WO of 5-15% 3; The TiO of 0.1-3% 2; The Sb of 0-0.2% 2o 3.
2. opticglass as claimed in claim 1, is characterized in that, described SiO 2: 2-6%.
3. opticglass as claimed in claim 1, is characterized in that, described B 2o 3: 12-15%.
4. opticglass as claimed in claim 1, is characterized in that, described La 2o 3: 27-32%.
5. opticglass as claimed in claim 1, is characterized in that, described Gd 2o 3: 13-17%.
6. opticglass as claimed in claim 1, is characterized in that, described Lu 2o 3be greater than 0 and be less than 2%.
7. opticglass as claimed in claim 1, is characterized in that, described La 2o 3/ (La 2o 3+ Gd 2o 3+ Lu 2o 3) below 0.65 and be greater than 0.60.
8. opticglass as claimed in claim 1, is characterized in that, described ZnO:10-13%.
9. opticglass as claimed in claim 1, is characterized in that, described Li 2o:0.2-1%.
10. opticglass as claimed in claim 1, is characterized in that, described ZrO 2: 1-6%.
11. opticglass as claimed in claim 1, is characterized in that, described WO 3: 8-13%.
12. opticglass as claimed in claim 1, is characterized in that, described TiO 2: 0.6-3%.
13. prefabricated part for mold pressing that adopt the opticglass described in the arbitrary claim of described 1-12 to form.
14. optical elements that adopt the opticglass described in the arbitrary claim of described 1-12 to form.
CN201110265549.XA 2011-09-08 2011-09-08 Optical glass, prefabricated member for mould pressing and optical element Active CN102424523B (en)

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PCT/CN2012/081039 WO2013034081A1 (en) 2011-09-08 2012-09-06 Optical glass, preform for moulding, and optical element
JP2014528841A JP5813233B2 (en) 2011-09-08 2012-09-06 Optical glass, preform for press molding, and optical element

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CN110028239B (en) * 2019-05-23 2022-08-09 成都光明光电股份有限公司 Optical glass, glass preform, optical element and optical instrument
CN111977970B (en) * 2020-09-07 2022-04-15 成都光明光电股份有限公司 Optical glass and optical element

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CN102424523A (en) 2012-04-25
WO2013034081A1 (en) 2013-03-14
JP2014527019A (en) 2014-10-09

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