CN102424523A - 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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Publication number
CN102424523A
CN102424523A CN201110265549XA CN201110265549A CN102424523A CN 102424523 A CN102424523 A CN 102424523A CN 201110265549X A CN201110265549X A CN 201110265549XA CN 201110265549 A CN201110265549 A CN 201110265549A CN 102424523 A CN102424523 A CN 102424523A
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glass
opticglass
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optical glass
content
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CN102424523B (en
Inventor
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 CN201110265549.XA priority Critical patent/CN102424523B/en
Publication of CN102424523A publication Critical patent/CN102424523A/en
Priority to JP2014528841A priority patent/JP5813233B2/en
Priority to PCT/CN2012/081039 priority patent/WO2013034081A1/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, more particularly, the present invention relates to a kind of high-refraction low-dispersion optical glass for mold, the prefabricated part for mold pressing that forms by said glass and the optical element that forms by said 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 the opticglass more than 37.But opticglass transmittance and specific refractory power are closely related usually, the high more often transmitance of specific refractory power variation, the aggravation of glass coloring tendency.
In addition, during the precise compression molding glass elements,, usually need under hot environment, carry out, the problems such as oxidation, corrosion of the forming face of mold often take place, be difficult to realize mass production at low cost.For this reason, the glass that uses in the precision moulded formation should have low transition temperature (Tg) as far as possible, and compression molding has also proposed higher requirement to the chemicalstability such as acidproof, water-fast of glass.
Summary of the invention
Technical problem to be solved by this invention provides a kind of specific refractory power more than 1.88, and Abbe number is the opticglass more than 37, and this opticglass transmitance is excellent, and transition temperature is low, is suitable for precision moulded formation.
The technical scheme that technical solution problem of the present invention is adopted is: opticglass, its weight percent content is: greater than 1% and less than 10% SiO 2The B of 10-20% 2O 3The La of 25-35% 2O 3The Gd of 10-20% 2O 3Greater than 0 and less than 5% Lu 2O 3Wherein, La 2O 3/ (La 2O 3+ Gd 2O 3+ Lu 2O 3) less than 0.67; The Ta of 10-20% 2O 5The ZnO of 8-15%; The LiO of 0.1-2% 2The ZrO of 0.5-8% 2The WO of 5-15% 3The TiO of 0.1-3% 2The Sb of 0-0.2% 2O 3
Further, said SiO 2: 2-6%.
Further, said B 2O 3: 12-15%.
Further, said La 2O 3: 27-32%.
Further, said Gd 2O 3: 13-17%.
Further, said Lu 2O 3Greater than 0 and less than 2%.
Further, said La 2O 3/ (La 2O 3+ Gd 2O 3+ Lu 2O 3) less than 0.67 and greater than 0.60.
Further, said ZnO:10-13%.
Further, said LiO 2: 0.2-1%.
Further, said ZrO 2: 1-6%.
Further, said 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, through adjustment La 2O 3, Gd 2O 3With Lu 2O 3Composition content, can obtain high refractive index and produce stable glass; Through control La 2O 3/ (La 2O 3+ Gd 2O 3+ Lu 2O 3) ratio, can obtain said optical constant and effectively improve the transmitance of said glass; The introducing of ZnO can reduce the transition temperature of glass, also can improve the chemicalstability 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 said glass.Optical glass refractive index scope of the present invention reaches more than 1.88, and the Abbe number scope is more than 37, and the glass transmitance is excellent, λ 70Below 385nm, glass transformation temperature is suitable for precise compression molding below 610 ℃, and can satisfy the imaging demand of optical system and equipment.
Embodiment
To carry out clear, intactly description to the technical scheme in the embodiment of the invention below, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
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 low excessively, then aforementioned DeGrain; SiO 2Too high levels, glass melting property variation then, transition temperature raises.Therefore, SiO 2Addition be greater than 1% and less than 10%, preferred content is greater than 1% less than 8%, more preferably content is 2%-6%.
As a kind of effective oxide that forms the glass network structure, B 2O 3It is the necessary component that obtains the low dispersion opticglass of high refraction.B among the present invention 2O can effectively improve glass melting property, reduces smelting temperature and viscous flow temperature.B 2O 3Content is too much, does not reach the high refractive index of said glass, and content is low excessively, and then glass is unstable; Therefore, require its content for being at least 10%, yet work as B 2O 3Content was greater than 20% o'clock, and specific refractory power descends, thereby can't 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 3Be the important component that obtains high-refractivity and low-dispersion glass, its content requirement is 25-35%, when its content is lower than 25%; Specific refractory power and low dispersivity all descend; When its greater than 35% the time, anti-increased devitrification resistance descends, and therefore can't stablize preparation glass; Preferred content is 27-32%, more preferably the scope of 28-32%.
Gd 2O 3Composition also has the specific refractory power that improves glass, the effect that makes its low chromatic dispersionization, and an amount of ratio ground uses Gd 2O 3, help to improve the anti-devitrification behavior of high refractive low dispersive glass.But if its amount is very few, then above-mentioned effect is insufficient, particularly can not get said Abbe number index; If its amount too much, then anti-increased devitrification resistance is variation on the contrary.Therefore, its content is 10-20%, and preferable range is 13-17%.
Lu 2O 3Be specific refractory power and the effective composition of increase Abbe number equally to improving glass., when containing too in a large number sometimes, make the forthright deterioration of anti-devitrification, specific gravity of glass increases; Lu 2O 3Also be a kind of expensive rare earth oxide simultaneously, therefore selected its content is greater than 0 less than 5%, and preferable range is less than 2% greater than 0.
The contriver is through discovering, with La with keen determination in the present invention 2O 3, Gd 2O 3With Lu 2O 3When three kinds high refraction rare earth oxides are introduced in the glass simultaneously, can effectively increase the low stable solubleness of chromatic dispersion oxide compound in glass of high refraction, especially, make said La through their content ratio of adjustment 2O 3/ (La 2O 3+ Gd 2O 3+ Lu 2O 3) scope satisfies less than 0.67, preferable range can make glass reach specific refractory power (nd) more than 1.88 less than 0.67 and greater than 0.60, and Abbe number is controlled at the optical constant 37 or more, and the light transmission of glass is excellent, can realize the batch stably manufactured; Above-mentioned effect especially added scope for greater than 0 less than 2% Lu 2O 3After more obvious.
Ta 2O 5Be the component that obtains high refractive index, can obviously improve the anti-increased devitrification resistance of glass simultaneously.But the too high Abbe number that will reduce glass of addition, it also is 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; It also is the necessary component that constitutes high-refractivity and low-dispersion glass; Can improve the anti-opacity of glass and reduce its viscous flow temperature, also have the glass chemistry of raising stability simultaneously and suppress the crystalline effect, its addition should be more than 8%; Otherwise said glass melting degradation, and chemicalstability worsens; But its content should be below 15%, otherwise can't 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 glass melting property, but usage quantity too much can reduce glass refraction, worsens stability, so its content 0.1-2%; Preferred 0.2-1%.
Add an amount of ZrO 2Can play and improve the anti-impervious effect of glass, but also can effectively reduce the high temperature viscosity of said glass, improve chemicalstability, ZrO 2Addition be at least 0.5%, otherwise do not reach effect, but its content should be below 8%, otherwise glass is prone to crystallization; Therefore its content is 0.5-8%, and preferred content is 1-6%, and more preferably content is 2-5%.
WO 3Composition has the raising glass refraction, improves the effect of devitrification of glass, and an amount of introducing can make glass make moderate progress at the light transmittance in the short wavelength zone of visible region; But in the present invention; If content is higher than 15%, transmitance on the contrary can variation, and the devitrification of glass performance depreciation.Therefore, its content is 5-15%, and preferred content is 8-13%.
In the present invention, introduce a spot of TiO 2Substitute WO 3Can make glass have higher specific refractory power, lower proportion, but as itself and WO 3During coexistence, if content is higher than 3%, the 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 used for glass melting is if but its content is too much, the transsmissivity variation in the short wavelength of visible region zone then.Therefore, can preferably contain as the upper limit with 0.2%, more preferably 0.1%, most preferably 0.05%.
According to the present invention, said opticglass preferably prepares according to following steps:
Oxide compound, oxyhydroxide, carbonate or nitrate salt with above-mentioned each component are raw material, and thorough mixing is placed in the platinum crucible, in 1200-1400 ℃, after preferred 1250-1350 ℃ of following fusing, clarification, the homogenizing, obtain melten glass;
Be poured in the metal pattern of preheating after reducing to said melten glass below 1100 ℃;
600 ℃ with the annealing of slowly lowering the temperature of the melten glass in the said metal pattern, thereby obtain opticglass.
Said opticglass is carried out performance test, and method is following:
Specific refractory power (nd) and Abbe number (υ d) value is the annealing value of-30 ℃/h, and specific refractory power and Abbe number are tested the specific refractory power of colouless optical glass and the testing method of abbe number according to what provide in " GB/T 7962.1-1987 ";
Glass is made the sample of 10mm ± 0.1mm thickness, and tested glass reaches 70% corresponding wavelength X 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 TR; 1 ℃ 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 the pairing 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; Transmittance reaches 70% o'clock corresponding wavelength X 70Below 385nm; Transition temperature is below 610 ℃.
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, preferred 37-40, more preferably 37-38; Transmittance reaches 70% o'clock corresponding wavelength X 70Below 385nm; Transition temperature reaches below 610 ℃, and is preferred below 605 ℃, more preferably below 602 ℃.
Opticglass of the present invention can be used as pressure forming with glass preshaping body material, perhaps also can be directly with the melten glass pressure forming.Method of manufacture and thermoforming process during as the glass preshaping body do not have special restriction, can use known method of manufacture and forming method.
In addition, also can carry out press working, make optical element, perhaps also can adopt directly fusion, remollescent opticglass are carried out press working, make optical element the glass preshaping body that opticglass of the present invention is made.
In addition, optical element can be used as for example 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 does not receive the qualification of these embodiment.
According to following steps, make opticglass according to the composition proportioning shown in the table 1-2:
Table 1-2 has provided embodiment glass and has formed.Respectively with raw material forms such as the corresponding oxide compound of each component, carbonate, nitrate salt, oxyhydroxide; Carry out weighing respectively according to making to become after its vitrifying to form shown in the table 1-2; Thorough mixing is placed in the platinum crucible; After 1250-1350 ℃ of following fusing, clarification, homogenizing, obtain melten glass;
Be poured in the metal pattern of preheating after reducing to said melten glass below 1100 ℃;
At 600 ℃ the melten glass in the said metal pattern is annealed, obtain opticglass.
Said opticglass is carried out performance test, and the result is referring to table 1-2, and table 1-2 is the performance perameter of the opticglass of embodiment of the invention preparation.
The proportioning raw materials of the opticglass of table 1: embodiment of the invention 1-5 preparation
Figure BDA0000090014460000051
Figure BDA0000090014460000061
The proportioning raw materials of the opticglass of table 2: embodiment of the invention 6-10 preparation
1-2 can know by table, and opticglass provided by the invention has high refractive index, the transmitance performance of excellence and good chemicalstability.

Claims (13)

1. opticglass is characterized in that, its weight percent content is: greater than 1% and less than 10% SiO 2The B of 10-20% 2O 3The La of 25-35% 2O 3The Gd of 10-20% 2O 3Greater than 0 and less than 5% Lu 2O 3Wherein, La 2O 3/ (La 2O 3+ Gd 2O 3+ Lu 2O 3) less than 0.67; The Ta of 10-20% 2O 5The ZnO of 8-15%; The LiO of 0.1-2% 2The ZrO of 0.5-8% 2The WO of 5-15% 3The TiO of 0.1-3% 2The Sb of 0-0.2% 2O 3
2. opticglass as claimed in claim 1 is characterized in that, said SiO 2: 2-6%.
3. opticglass as claimed in claim 1 is characterized in that, said B 2O 3: 12-15%.
4. opticglass as claimed in claim 1 is characterized in that, said La 2O 3: 27-32%.
5. opticglass as claimed in claim 1 is characterized in that, said Gd 2O 3: 13-17%.
6. opticglass as claimed in claim 1 is characterized in that, said Lu 2O 3Greater than 0 and less than 2%.
7. opticglass as claimed in claim 1 is characterized in that, said La 2O 3/ (La 2O 3+ Gd 2O 3+ Lu 2O 3) less than 0.67 and greater than 0.60.
8. opticglass as claimed in claim 1 is characterized in that, said ZnO:10-13%.
9. opticglass as claimed in claim 1 is characterized in that, said LiO 2: 0.2-1%.
10. opticglass as claimed in claim 1 is characterized in that, said ZrO 2: 1-6%.
11. opticglass as claimed in claim 1 is characterized in that, said WO 3: 8-13%.
12. the prefabricated part for mold pressing that adopts the described opticglass of the arbitrary claim of said 1-11 to form.
13. the optical element that adopts the described opticglass of the arbitrary claim of said 1-11 to form.
CN201110265549.XA 2011-09-08 2011-09-08 Optical glass, prefabricated member for mould pressing and optical element Active CN102424523B (en)

Priority Applications (3)

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CN201110265549.XA CN102424523B (en) 2011-09-08 2011-09-08 Optical glass, prefabricated member for mould pressing and optical element
JP2014528841A JP5813233B2 (en) 2011-09-08 2012-09-06 Optical glass, preform for press molding, and optical element
PCT/CN2012/081039 WO2013034081A1 (en) 2011-09-08 2012-09-06 Optical glass, preform for moulding, and optical element

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Cited By (1)

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CN110028239A (en) * 2019-05-23 2019-07-19 成都光明光电股份有限公司 Optical glass, gas preform, optical element and optical instrument

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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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CN101759359A (en) * 2009-12-25 2010-06-30 成都光明光电股份有限公司 High-refraction low-dispersion optical glass for mold pressing

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EP0266812A1 (en) * 1986-10-08 1988-05-11 Koninklijke Philips Electronics N.V. Luminescent alumino-silicate and/or alumino-borate glass comprising lanthanum and/or gadolinium and luminescent screen provided with such a glass
JPH08217484A (en) * 1995-02-13 1996-08-27 Ohara Inc Optical glass
CN1935717A (en) * 2006-10-17 2007-03-28 成都光明光电股份有限公司 Optical glass for high-refractivity low dispersion precision die mould
CN101239780A (en) * 2007-01-24 2008-08-13 Hoya株式会社 Optical glass, preformed member for precision press-molding, optical element, and methods for manufacturing the same
CN101759359A (en) * 2009-12-25 2010-06-30 成都光明光电股份有限公司 High-refraction low-dispersion optical glass for mold pressing

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Publication number Priority date Publication date Assignee Title
CN110028239A (en) * 2019-05-23 2019-07-19 成都光明光电股份有限公司 Optical glass, gas preform, optical element and optical instrument

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WO2013034081A1 (en) 2013-03-14
JP5813233B2 (en) 2015-11-17
JP2014527019A (en) 2014-10-09

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