CN102923951B - Optical glass and optical element - Google Patents

Optical glass and optical element Download PDF

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Publication number
CN102923951B
CN102923951B CN201210480110.3A CN201210480110A CN102923951B CN 102923951 B CN102923951 B CN 102923951B CN 201210480110 A CN201210480110 A CN 201210480110A CN 102923951 B CN102923951 B CN 102923951B
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glass
optical glass
optical
content
temperature
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CN102923951A (en
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匡波
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Chengdu Guangming Optoelectronics Co Ltd
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Chengdu Guangming Optoelectronics 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
    • C03C4/00—Compositions for glass with special properties
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/002—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (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)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)

Abstract

The present invention provides a kind of inexpensive optical glass for precision profiling, which does not contain Gd2O3Component, density 4.2g/cm3Hereinafter, refractive index is 1.71~1.78, and Abbe number is 45~55, and transition temperature is less than 550 DEG C.The present invention is added without expensive Gd by the content of reasonable arrangement each component2O3, production cost is reduced, has saved resource.The transmittance of the optical glass of the present invention reaches corresponding wavelength X when 80%80For below 370nm；Crystallization ceiling temperature is below 1050 DEG C；Water resistance is used up to 1 grade suitable for precise compression molding.

Description

Optical glass and optical element
Technical field
The present invention relates to the accurate die pressing optical glass that a kind of refractive index is 1.71~1.78, Abbe number is 45~55, And the optical element made of the optical glass.
Background technology
In recent years, with the quick popularization and use of digital camera, video camera and camera mobile phone so that optical material Also developed rapidly towards the direction of high precision int, miniaturization.To meet requirements above, optical design is carried out using non-spherical lens As mainstream.Increasingly it is taken seriously on Optical element manufacturing with low cost, the precise compression molding technology of high yield.
When carrying out precise compression molding, in order to which high-accuracy die face is replicated on glass products formed, it is necessary in high temperature Under（15~40 DEG C usually more than glass softening point temperature）Glass preform is press-formed, at this moment shaping mould is exposed in high temperature And higher pressure is subjected to, even in protective atmosphere, casted die mould surface mold layer is still oxidized easily erosion.It is accurate In compression molding, high-accuracy mould is main cost source, and mould cannot be realized using certain access times are not reached The purpose of inexpensive high yield.In order to extend the service life of mould, damage of the hot environment to molding die is reduced, then is needed Die mould temperature is reduced as much as possible.It is therefore desirable to the transition temperature of glass material（Tg）Low as far as possible, this allows for being suitable for essence The demand of the low softening point optical glass of close die mould is growing day by day.
It is cost-effective not only can be by extending the molding die service life, it is also crucial to reduce cost of material. CN02155831.0 discloses a kind of optical glass, wherein containing expensive Gd2O3, cause the cost of the optical glass very It is high.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of inexpensive optical glass for precision profiling, the optics glass The density of glass（ρ）For 4.2g/cm3Hereinafter, refractive index（nd）For 1.71~1.78, Abbe number（vd）For 45~55, transition temperature （Tg）For less than 550 DEG C.
The technical proposal for solving the technical problem of the invention is：Optical glass, does not contain Gd2O3Component, density are 4.2g/cm3Hereinafter, refractive index is 1.71~1.78, and Abbe number is 45~55, and transition temperature is less than 550 DEG C.
Further, its percentage by weight composition is：SiO2：1~10%, B2O3：22~35%, La2O3：26~38%, ZrO2：1~8%, ZnO：20~30%, CaO：0~3%, SrO：0~3%, Ta2O5：0.1~5%, Y2O3：1~10%, Li2O:0.1~ 3%。
Further, wherein：SiO2：2~5%.
Further, wherein：B2O3：25~30%, La2O3：30~35%.
Further, wherein：ZrO2：1~5%.
Further, wherein：ZnO：22~27%.
Further, wherein：Ta2O5：0.5~2.5%.
Further, wherein：Y2O3：3~7%.
Optical glass, its percentage by weight composition are：SiO2：1~10%, B2O3：22~35%, La2O3：26~38%, ZrO2：1~8%, ZnO：20~30%, CaO：0~3%, SrO：0~3%, Ta2O5：0.1~5%, Y2O3：1~10%, Li2O:0.1~ 3%。
Further, wherein：SiO2：2~5%.
Further, wherein：B2O3：25~30%, La2O3：30~35%.
Further, wherein：ZrO2：1~5%.
Further, wherein：ZnO：22~27%.
Further, wherein：Ta2O5：0.5~2.5%.
Further, wherein：Y2O3：3~7%.
Using gas preform made of above-mentioned optical glass.
Using optical element made of above-mentioned optical glass.
Using optical instrument made of above-mentioned optical glass.
The beneficial effects of the invention are as follows：The present invention is added without expensive by the content of reasonable arrangement each component Gd2O3, production cost is reduced, has saved resource.The optical glass density of the present invention（ρ）For 4.2g/cm3Below；Refractive index （nd）For 1.71~1.78；Abbe number（vd）For 45~55；Transition temperature（Tg）For less than 550 DEG C；When transmittance reaches 80% pair The wavelength X answered80For below 370nm；Crystallization ceiling temperature is below 1050 DEG C；Water resistance is used up to 1 grade suitable for precise compression molding.
Embodiment
Each component of optical glass of the present invention is described below, unless otherwise indicated, the ratio of each component content is Represented with weight %.
SiO2It is the network generation oxide body to form glass, adds a certain amount of SiO2The high temperature viscosity of glass can be increased, Improve the devitrification resistance property of glass.SiO2Content more than 10% when, the meltability of optical glass reduces, softening temperature rise.Cause This SiO2Content be defined to 1~10%, be preferably 2~5%.
As a kind of effective oxide for forming glass network structure, B2O3It is to obtain high refraction, the group of the lanthanides optics of low dispersion The necessary component of glass.B in the present invention2O3The meltbility of glass can be efficiently modified, reduces smelting temperature and viscous flow temperature.When B2O3When content is less than 22%, it is difficult to obtain the glass of property stabilization, devitrification resistance property is undesirable；But work as B2O3Content is higher than 35% When, the refractive index of glass does not reach design object, while the chemical stability of glass can reduce.Therefore, B2O3Content be defined to 22~35%, more preferably content is 25~30%.
La2O3It is high refraction, the main component of low-dispersion optical glass for mold, the refractive index and unobvious that can increase glass carry The dispersion of high glass, in inventive formulation system, B2O3With La2O3Combination exist, the resistance to mistake of glass can be effectively improved Permeability energy, improves the chemical stability of glass.Work as La2O3Content be less than 26% when, it is impossible to obtain the effect of the above；When its content During more than 38%, the crystallization property of glass deteriorates, therefore its content is defined to 26~38%, and preferred content is 30~35%.
ZrO2The viscosity, hardness and chemical stability of glass can be improved, reduces the thermal coefficient of expansion of glass.ZrO2Content During more than 8%, glass infusibility, easy devitrification, and also chemical durability of glass deteriorates.Therefore ZrO2Content preferably 1~8%, it is more excellent Elect 1~5% as.
ZnO is the important component to form low-melting point optical glass, can reduce the thermal coefficient of expansion of glass, improve glass Chemical stability, heat endurance and refractive index.When the content of ZnO is more than 30%, the easy devitrification of optical glass；When the content of ZnO During less than 20%, the transition temperature rise of optical glass.Therefore, the content of ZnO is preferably 20~30%, and more preferably 22~27%.
CaO has improvement stability, glass, and the effect of melting sources is helped during melting production, but its content is higher than 3% When glass tendency towards devitrification increase, therefore the content of CaO is defined to 0~3%.
The effects of SrO in glass are similar to BaO, replace part BaO to accelerate the fusing and clarification of glass with SrO, drop The tendency towards devitrification of low glass, when its content is higher than 3%, is melted difficulty, therefore SrO contents are defined to 0~3%, preferably 0~ 1%, more preferably it is added without.
Ta2O5Be to confer to the component of the high refraction of optical glass and low dispersion characteristics, can effective reinforcing glass stability, But Ta2O5Content is high, the increase of glass cost.Therefore Ta2O5Content be preferably 0.1~5%, more preferably 0.5~2.5%.
Y2O3With the effect for improving refractive index, reducing dispersion, but if its content is excessive, devitrification resistance property is drastically Ground reduces.Therefore, Y2O3Preferred content be 1~10%, more preferably content be 3~7%.
Li2O can effectively reduce glass transformation temperature, be effectively improved the thawing ability of glass, reduce fusion temperature, at the same time It can also effectively reduce glass density；But deteriorate the processing performance of glass as its content Gao Shihui, the devitrification resistance of glass and Chemical stability declines, so Li2The preferred content of O is 0.1~3%.
The performance of optical glass of the present invention is described below.
Density according to by《GB/T 7962.20-1987 colouless optical glass test method density measurement methods》Test.
Refractive index and Abbe number according to《The colouless optical glass test method refractive index of GB/T 7962.1-1987 and dispersion Coefficient》Test.
Transition temperature（Tg）According to《GB/T7962.16-1987 colouless optical glass test methods linear expansion coefficient, transformation Temperature and slackened temperature》Test, i.e.,：Sample is within the scope of certain temperature, and temperature often raises 1 DEG C, in sample On expansion curve, low-temperature region and high-temperature area straight line portion are extended into intersecting, the temperature corresponding to its intersection point.
Glass is fabricated to the sample of 10mm ± 0.1mm thickness, test glass reaches 80% corresponding wavelength in transmittance λ80。
Using the crystallization property of temperature gradient furnace method measure glass, glass is made to the sample of 180 × 10 × 10mm, side is thrown Light, be put into the stove inside holding 4 with temperature gradient it is small when after take out, under the microscope observe devitrification of glass situation, glass occur The corresponding maximum temperature of crystal is the crystallization ceiling temperature of glass.
Water-fast effect stability DW（Powder method）By the test method of GB/T17129, calculate according to the following formula：
DW=（B-C）/（B-A）×100
In formula：DW- glass leaches percentage（%）
The quality of B-filter and sample（g）
The quality of sample after C-filter and erosion（g）
A-filter quality（g）
By the leaching percentage being calculated, D is stablized into the water-fast effect of optical glassWIt is divided into 6 classes see the table below.
By test, optical glass provided by the invention has the following performance：Density（ρ）For 4.2g/cm3Below；Refraction Rate（nd）For 1.71~1.78；Abbe number（vd）For 45~55；Transition temperature（Tg）For less than 550 DEG C；When transmittance reaches 80% Corresponding wavelength X80For below 370nm；Crystallization ceiling temperature is below 1050 DEG C；Water resistance is up to 1 grade.
The present invention also provides a kind of optical element, by above-mentioned optical glass according to method shape well known to those skilled in the art Into.Since the optical glass has high index of refraction and relatively low glass transformation temperature, the optical element also has High index of refraction and relatively low glass transformation temperature, can be applied to the equipment such as digital camera, digital camera, camera cell phone.
Embodiment
In order to further appreciate that technical scheme, the embodiment of optical glass of the present invention will now be described.Should It is noted that these embodiments do not limit the scope of the invention.
The optical glass shown in 1~table of table 3（Embodiment 1~30）It is by according to each embodiment shown in 1~table of table 3 Ratio weigh and hybrid optical glass common raw material（Such as oxide, hydroxide, carbonate, nitrate and fluoride）, Mixed material is placed in platinum crucible, is melted in 1100~1300 DEG C of temperature, and through melting, clarifying, stirring After homogenizing, obtain no bubble and the homogeneous melt glass without undissolved material, by this melten glass in mould casting mold And anneal and form.
The composition and refractive index of the embodiment of the present invention 1~30（nd）, Abbe number（vd）, density（ρ）, glass transformation temperature （Tg）, crystallization ceiling temperature, water resistance and transmittance reach corresponding wavelength X when 80%80The result table in 1~table of table 3 together Show.In these tables, the composition of each component is represented with weight %.
Table 1
Table 2
Table 3
From above-described embodiment as can be seen that the optical glass density of the present invention（ρ）For 4.2g/cm3Below；Refractive index（nd） For 1.71~1.78；Abbe number（vd）For 45~55；Transition temperature（Tg）For less than 550 DEG C；Transmittance reaches corresponding when 80% Wavelength X80For below 370nm；Crystallization ceiling temperature is below 1050 DEG C；Water resistance is used up to 1 grade suitable for precise compression molding.

Claims (16)

1. optical glass, it is characterised in that do not contain Gd2O3Component, density 4.2g/cm3Hereinafter, refractive index for 1.71~ 1.78, Abbe number is 45~55, and transition temperature is less than 550 DEG C, La2O3：26~38%, ZnO：20.1~30%, Y2O3：1~ 7.71%, SiO2：More than 5% but it is less than or equal to 10%, B2O3：25~35%, without WO3, Li2O：0.1~2.5%.
2. optical glass as claimed in claim 1, it is characterised in that its percentage by weight, which forms, is：SiO2：It is more than 5% but small In or equal to 10%, B2O3：25~35%, La2O3：26~38%, ZrO2：1~8%, ZnO：20.1~30%, CaO：0~ 3%th, SrO：0~3%, Ta2O5：0.1~5%, Y2O3：1~7.71%, Li2O：0.1~2.5%.
3. optical glass as claimed in claim 1 or 2, it is characterised in that wherein：B2O3：25~30%, La2O3：30~ 35%.
4. optical glass as claimed in claim 1 or 2, it is characterised in that wherein：ZrO2：1~5%.
5. optical glass as claimed in claim 1 or 2, it is characterised in that wherein：ZnO：22~27%.
6. optical glass as claimed in claim 1 or 2, it is characterised in that wherein：Ta2O5：0.5~2.5%.
7. optical glass as claimed in claim 1 or 2, it is characterised in that wherein：Y2O3：3~7%.
8. optical glass, it is characterised in that its percentage by weight, which forms, is：SiO2：More than 5% but less than or equal to 10%, B2O3：25~35%, La2O3：26~38%, ZrO2：1~8%, ZnO：20.1~30%, CaO：0~3%, SrO：0~3%, Ta2O5：0.1~5%, Y2O3：1~7.71%, Li2O：0.1~2.5%.
9. optical glass as claimed in claim 8, it is characterised in that wherein：B2O3：25~30%, La2O3：30~35%.
10. optical glass as claimed in claim 8, it is characterised in that wherein：ZrO2：1~5%.
11. optical glass as claimed in claim 8, it is characterised in that wherein：ZnO：22~27%.
12. optical glass as claimed in claim 8, it is characterised in that wherein：Ta2O5：0.5~2.5%.
13. optical glass as claimed in claim 8, it is characterised in that wherein：Y2O3：3~7%.
14. using gas preform made of the optical glass described in any claim in claim 1-13.
15. optical element made of the optical glass as described in claim 1-13 any claims.
16. optical instrument made of the optical glass as described in claim 1-13 any claims.
CN201210480110.3A 2012-11-23 2012-11-23 Optical glass and optical element Active CN102923951B (en)

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CN110963700B (en) * 2018-09-28 2022-11-22 成都光明光电股份有限公司 Optical glass, preform thereof, optical element and optical instrument
CN109761489B (en) * 2019-03-28 2022-04-12 成都光明光电股份有限公司 Optical glass

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JP3458461B2 (en) * 1994-07-07 2003-10-20 株式会社ニコン Optical glass
US8507394B2 (en) * 2005-04-22 2013-08-13 Ohara Inc. Glass composition
JP5561888B2 (en) * 2005-10-11 2014-07-30 株式会社オハラ Optical glass
JP4746995B2 (en) * 2006-02-02 2011-08-10 株式会社オハラ Optical glass
CN1935717B (en) * 2006-10-17 2010-10-06 成都光明光电股份有限公司 Optical glass for high-refractivity low dispersion precision die mould
JP4997990B2 (en) * 2007-01-24 2012-08-15 コニカミノルタアドバンストレイヤー株式会社 Optical glass and optical element
CN101439929B (en) * 2008-12-24 2011-09-07 成都光明光电股份有限公司 Optical glass, prefabricated part for precise compression molding and optical element
KR20110001972A (en) * 2009-06-30 2011-01-06 가부시키가이샤 오하라 Optical glass, preform material and optical device
CN102153279B (en) * 2010-02-12 2013-11-06 肖特玻璃科技(苏州)有限公司 Optical glass for precision molding
CN101805120B (en) * 2010-04-19 2013-02-20 成都光明光电股份有限公司 Optical glass and optical element

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