CN107698142A - Optical glass, optical precast product and optical element - Google Patents

Optical glass, optical precast product and optical element Download PDF

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Publication number
CN107698142A
CN107698142A CN201710879579.7A CN201710879579A CN107698142A CN 107698142 A CN107698142 A CN 107698142A CN 201710879579 A CN201710879579 A CN 201710879579A CN 107698142 A CN107698142 A CN 107698142A
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CN
China
Prior art keywords
optical glass
glass
optical
content
cao
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710879579.7A
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Chinese (zh)
Inventor
孙伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CDGM Glass Co Ltd
Chengdu Guangming Optoelectronics Co Ltd
Original Assignee
Chengdu Guangming Optoelectronics Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chengdu Guangming Optoelectronics Co Ltd filed Critical Chengdu Guangming Optoelectronics Co Ltd
Priority to CN201710879579.7A priority Critical patent/CN107698142A/en
Publication of CN107698142A publication Critical patent/CN107698142A/en
Pending legal-status Critical Current

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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
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • 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
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
    • 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

Abstract

The present invention provides a kind of PbO, As for not containing pollution environment2O3With the optical glass of fluoride, its refractive index is 1.48~1.56, and Abbe number is 55~65.Optical glass, its composition include by weight percentage：SiO2：60~80%, TiO2：0~3%, BaO：0~5%, CaO：5.5~15%, B2O3：0~3%, Sb2O3：0~1%, Na2O:5~15%, K2O：5~15%, ZnO：0~10%, but do not contain Li2O.The present invention makes Optical Glass Chemical Stability Test excellent, the density of obtained environmental protection optical glass is 2.8g/cm by the content of Reasonable adjustment glass ingredient3Hereinafter, moisture resistant atmospheric action stability RC (S) is 1 grade, and antiacid effect stability RA (S) is more than 3 grades, and mean thermal expansion coefficients α is 100 × 10‑7/ DEG C below.

Description

Optical glass, optical precast product and optical element
The application is to be directed to Application No. 201310168237.6, and the applying date is on May 9th, 2013, entitled " optics glass The divisional application of the application for a patent for invention of glass, optical precast product and optical element ".
Technical field
The present invention relates to a kind of optical glass, more particularly to a kind of refractive index (nd) it is 1.48~1.56, Abbe number (νd) For 55~65 optical glass, and prefabricated component, optical element and the optical instrument being made up 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, this allows for having low refraction, low-density Optical glass demand it is increasing.Today grown to even greater heights to the cry of environmental protection, to the environmental protection of optical glass Also into the direction of product development.Though use in the past and manufacture the conventional pollutant component lead oxide of optical glass and arsenic oxide arsenoxide etc. Substituted by other components, but simply replace lead oxide and arsenic oxide arsenoxide with one or more of components, product differ surely into Reproduce optical property and physical and chemical performance as caused by lead oxide and arsenic oxide arsenoxide work(.Therefore, to the new research of glass composition It is necessary with substance research and development.
CN99110919.8 discloses a kind of lead-free optic glass, and it contains a certain amount of fluoride, in actual production Cheng Zhong, fluoride gas and dust can be discharged, pollute environment, the glass also contains substantial amounts of B in addition2O3, this can cause glass to exist Volatility increases during thawing, while the devitrification resistance of glass is deteriorated.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of PbO, As for not containing pollution environment2O3With fluoride Optical glass, its refractive index are 1.48~1.56, and Abbe number is 55~65.
The technical proposal for solving the technical problem of the invention is：Optical glass, its composition include by weight percentage： SiO2：60~80%, TiO2：0~3%, BaO：0~5%, CaO：5.5~15%, B2O3：0~3%, Sb2O3：0~1%, Na2O:5~15%, K2O：5~15%, ZnO：0~10%, but do not contain Li2O。
Optical glass, its composition are by weight percentage：SiO2：60~80%, TiO2：0~3%, BaO：0~5%, CaO：5.5~15%, B2O3：0~3%, Sb2O3：0~1%, Na2O:5~15%, K2O：5~15%, ZnO：0~10%.
Further, wherein：Na2O and K2O total amount：10~19%.
Further, wherein：SiO2：65~75%.
Further, wherein：TiO2：0~2%.
Further, wherein：BaO：0.5~3%.
Further, wherein：CaO：5.5~12%.
Further, wherein：B2O3：0~2%.
Further, wherein：Na2O:8~15%.
Further, wherein：K2O：5~10%.
Further, wherein：ZnO：3.5~8%.
Further, the optical glass moisture resistant atmospheric action stability RC is 1 grade, and antiacid effect stability RA is 3 It is more than level.
Further, the optical glass density is 2.8g/cm3Hereinafter, mean thermal expansion coefficients α (20~300 DEG C) is 100×10-7/ DEG C below.
Further, the optical glass refractive index is 1.48~1.56, and Abbe number is 55~65.
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：PbO, As are added without in the component of the present invention2O3And fluoride, and by rationally adjusting The content of other whole glass ingredients, make Optical Glass Chemical Stability Test excellent, the density of obtained environmental protection optical glass is 2.8g/ cm3Hereinafter, refractive index is 1.48~1.56, and Abbe number is 55~65, and moisture resistant atmospheric action stability RC (S) is 1 grade, antiacid It is more than 3 grades to act on stability RA (S), and (20~300 DEG C) of mean thermal expansion coefficients α is 100 × 10-7/ DEG C below.
Embodiment
Each component of optical glass of the present invention is described below, unless otherwise indicated, the ratio of each constituent content is Represented with weight %.
SiO2It is important glass former oxide, skeleton function is played in glass structure, is that optical glass realizes light Learn constant basis, its content number it is closely related with the chemical stability and melt characteristic of glass.In the present invention, when SiO2When content is less than 60%, the chemical stability of glass can reduce；But when its content is more than 80%, then it is difficult to maintain glass Optical constant, while can also significantly improve the melt temperature of glass.In order to obtain the especially excellent glass of chemical stability, together When take into account its melt characteristic, SiO of the invention2Content is 60~80%, preferably 65~75%.
B2O3And the oxide of glass is formed, when its content is more than 5%, the refractive index of glass is too low, in fusion process Volatility increases, and causes the optical constant fluctuation of glass and the chemical stability of glass is deteriorated, to obtain having desired light Learn constant range and the optical glass with excellent chemical stability, B2O3Content be defined to 0~3%, preferred content 0 ~2%.
TiO2The water resistance of glass can be improved, reduces specific gravity of glass, but its too high levels can cause glass coloration.Therefore TiO2Content be defined to 0~3%, preferred content is 0~2%.
BaO can adjust the refractive index and Abbe number of glass, chemical durability of glass and heat endurance be improved, when its content During more than 5%, the Abbe number increase of glass, the tendency towards devitrification increase of glass, therefore, BaO content is preferably 0~5%, preferably For 0.5~3%.
CaO can improve chemical durability, reduce and maintain average coefficient of linear expansion, while can also reduce the transformation temperature of glass Degree, but when its content is excessive, liquidus temperature easily rises.Therefore, CaO content is defined to 5.5~15%, preferred content 5.5 ~12%.
Na2O can effectively improve the meltdown property and adjustment optical constant of glass, if the content of this component is less than 5%, Then can not fully obtain these effects, and if the content of this component more than 15%, then the chemical stability of glass is significantly deteriorated. Therefore, the content of this component is defined to 5~15%, preferably 8~15%.
K2O is used for the optical constant for adjusting glass and the crystallization property for reducing glass.When its content is less than 5%, nothing Method reaches the effect above；If content more than 15%, can cause the deterioration of chemical durability of glass.Therefore, K2O content be 5~ 15%, preferably 5~10%.
The present invention is added without Li2O, pass through Na2O and K2O mixed alkali effect improves the chemical stability of glass, Na2O and K2O total content is defined to 10~19%.
ZnO can improve the meltbility and chemical durability of glass, can particularly improve the water resistance of glass.When containing for ZnO Measure as less than 10%, the meltbility and transmittance of glass can be significantly improved, therefore, ZnO content of the invention is 0~10%, excellent Elect 3.5~8% as.
Sb2O3Used in the present invention as fining agent, its content range is 0~1%.
The present invention can also add ZrO in right amount2, it can improve the chemical stability of glass, reduce the thermal coefficient of expansion of glass.
The present invention can also add both alkaline earth oxides of MgO and SrO, its effect, Ke Yiti similar with CaO in right amount The chemical durability of high glass.
The performance of the optical glass of the present invention is described below.
Refractive index and Abbe number according to《The colouless optical glass method of testing refractive indexes of GB/T 7962.1-1987 and dispersion Coefficient》Test.
Density according to《GB/T 7962.20-1987 colouless optical glass method of testing density measurement methods》Test.
Moisture resistant atmospheric action stability RC (S) (surface method)：It is three-level according to the analysis of stability acted on moist atmosphere, Wherein：
1 grade：Under conditions of temperature 50 C, relative humidity 85%, the time that glass polishing surface forms hydrolysis spot surpasses Cross 20h；
2 grades：Under conditions of temperature 50 C, relative humidity 85%, glass polishing surface forms the time of hydrolysis spot 5 ~20h；
3 grades：Under conditions of temperature 50 C, relative humidity 85%, glass polishing surface forms the time of hydrolysis spot not To 5h.
Antiacid effect stability RA (S) (surface method)：It is three-level according to the analysis of stability acted on acid solution, wherein：
1 grade：Under the acetum effect of 0.1N (equivalent concentration), temperature 50 C, the collapse dept on glass polishing surface Up to 135nm time more than 5h；
2 grades：Under the acetum effect of 0.1N, temperature 50 C, the collapse dept on glass polishing surface up to 135nm when Between in 1~5h；
3 grades：Under the acetum effect of 0.1N, temperature 50 C, the collapse dept on glass polishing surface up to 135nm when Between less than 1h.
The average value that thermalexpansioncoefficientα method measurement temperature as defined in GB/T7962.16-2010 is 20~300 DEG C.
By test, optical glass of the invention has following performance：Density is 2.8g/cm3Hereinafter, refractive index (nd) be 1.48~1.56；Abbe number (νd) it is 55~65；Moisture resistant atmospheric action stability RC (S) is 1 grade；Antiacid effect stability RA (S) it is more than 3 grades, preferably more than 2 grades, more preferably 1 grade；(20~300 DEG C) of mean thermal expansion coefficients α is 100 × 10-7/℃ Below.
The present invention also provides a kind of optical precast product and optical element, by above-mentioned optical glass according to those skilled in the art Well known method is formed, and described optical precast product and optical element can apply to digital camera, digital camera, The equipment such as camera cell phone.
Embodiment
In order to further appreciate that technical scheme, the embodiment of optical glass of the present invention is described below, it should It is noted that these embodiments do not limit the scope of the present invention.
The embodiment 1~30 shown in 1~table of table 3 is weighed by the ratio according to each embodiment shown in 1~table of table 3 And mixed material is placed on common raw material (such as oxide, hydroxide, carbonate and nitrate) by hybrid optical glass In crucible, melted in certain temperature, and after melting, clarify, stirring and being homogenized, obtain no bubble and without not molten Solve material homogeneous melt glass, by this melten glass in mould casting mold and anneal form.
The composition of the embodiment of the present invention 1~30 and refractive index (nd), Abbe number (vd), density (ρ), moisture resistant atmospheric action Stability RC (S), antiacid effect stability RA (S), mean thermal expansion coefficients α result represent in 1~table of table 3 together. In these tables, the composition of each component is represented with percentage by weight.
Table 1
Table 2
Table 3
Glass of the present invention can be seen that by the embodiment in above-mentioned table 1- tables 3 and be added without PbO, As2O3And fluoride, obtain The optical glass density arrived is 2.8g/cm3Below；Refractive index (nd) it is 1.48~1.56；Abbe number (νd) it is 55~65；Moisture resistance Damp atmosphere effect stability RC (S) is 1 grade；Antiacid effect stability RA (S) is more than 3 grades, preferably 2 grades, more preferably 1 grade； (20~300 DEG C) of mean thermal expansion coefficients α is 100 × 10-7/ DEG C below.

Claims (11)

1. optical glass, it is characterised in that its composition includes by weight percentage：SiO2：60~80%, CaO：5.5~15%, Na2O：5~15%, K2O：5~15%, ZnO：0~10%, but do not contain Li2O。
2. optical glass, it is characterised in that its composition includes by weight percentage：SiO2：60~80%, CaO：5.5~15%, B2O3：0~3%, Na2O：5~15%, K2O：5~15%, ZnO：0~10%.
3. optical glass as claimed in claim 1 or 2, it is characterised in that its composition represents by weight percentage, in addition to： TiO2：0~3%, BaO：0~5%, B2O3：0~3%, Sb2O3：0~1%.
4. optical glass as claimed in claim 1, it is characterised in that its composition is by weight percentage：SiO2：60~80%, TiO2：0~3%, BaO：0~5%, CaO：5.5~15%, B2O3：0~3%, Sb2O3：0~1%, Na2O：5~15%, K2O： 5~15%, ZnO：0~10%.
5. the optical glass as described in Claims 1 to 4 any claim, it is characterised in that wherein：Na2O and K2O's is total Amount：10~19%.
6. the optical glass as described in Claims 1 to 4 any claim, it is characterised in that wherein：SiO2：65~75%； And/or TiO2：0~2%；And/or BaO：0.5~3%；And/or CaO：5.5~12%；And/or B2O3：0~2%；And/or Na2O：8~15%；And/or K2O：5~10%；And/or ZnO：3.5~8%.
7. the optical glass as described in claim 1~6 any claim, it is characterised in that the moisture resistance of the optical glass Damp atmosphere effect stability RC (S) is 1 grade, and antiacid effect stability RA (S) is more than 3 grades, and the optical glass density is 2.8g/cm3Hereinafter, (20~300 DEG C) of mean thermal expansion coefficients α is 100 × 10-7/ DEG C below.
8. the optical glass as described in claim 1~6 any claim, it is characterised in that the optical glass refractive index For 1.48~1.56, Abbe number is 55~65.
9. using gas preform made of the optical glass described in any claim in claim 1~8.
10. using optical element made of the optical glass described in any claim in claim 1~8.
11. using optical instrument made of the optical glass described in any claim in claim 1~8.
CN201710879579.7A 2013-05-09 2013-05-09 Optical glass, optical precast product and optical element Pending CN107698142A (en)

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CN201710879579.7A CN107698142A (en) 2013-05-09 2013-05-09 Optical glass, optical precast product and optical element

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CN201310168237.6A CN104140204A (en) 2013-05-09 2013-05-09 Optical glass, optical preform and optical element
CN201710879579.7A CN107698142A (en) 2013-05-09 2013-05-09 Optical glass, optical precast product and optical element

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CN105819683B (en) * 2016-03-04 2019-12-03 成都光明光电股份有限公司 Environmental protection optical glass and optical element
CN106396373A (en) * 2016-08-26 2017-02-15 湖北戈碧迦光电科技股份有限公司 Functional optical glass, and preparation method and applications thereof

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SU948919A1 (en) * 1980-12-23 1982-08-07 Предприятие П/Я Р-6681 Optical glass
JPH04224132A (en) * 1990-12-25 1992-08-13 Nippon Electric Glass Co Ltd Optical glass
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