CN107473584A - Environmental protection optical glass, gas preform, optical element and optical instrument - Google Patents

Environmental protection optical glass, gas preform, optical element and optical instrument Download PDF

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Publication number
CN107473584A
CN107473584A CN201710874397.0A CN201710874397A CN107473584A CN 107473584 A CN107473584 A CN 107473584A CN 201710874397 A CN201710874397 A CN 201710874397A CN 107473584 A CN107473584 A CN 107473584A
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China
Prior art keywords
glass
environmental protection
optical glass
optical
protection optical
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CN201710874397.0A
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Chinese (zh)
Inventor
毛露路
匡波
孙伟
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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 CN201710874397.0A priority Critical patent/CN107473584A/en
Publication of CN107473584A publication Critical patent/CN107473584A/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
    • C03C3/076—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
    • 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

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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 one kind and does not contain expensive Nb2O5And Li2O, and the PbO and As of pollution environment2O3, while optical property meets that refractive index is 1.58~1.65, Abbe number is 40~50 environmental protection optical glass.Environmental protection optical glass, by weight percentage composition are：SiO2：40~60%, B2O3：1~10%, BaO：12~32%, ZnO：1~8%, TiO2：2~12%, K2O：2~12%, Na2O:1~8%, CaO：0~8%, ZrO2：0~5%, Sb2O3：0~0.1%.The present invention passes through Reasonable adjustment TiO2Component, make the light transmission rate of glass excellent, transmittance reaches corresponding wavelength X when 80%80Less than 390nm, transmittance reaches corresponding wavelength X when 5%5Less than 350nm.

Description

Environmental protection optical glass, gas preform, optical element and optical instrument
The application is to be directed to Application No. 201310058615.5, and the applying date is on 2 25th, 2013, entitled " environmental protection The divisional application of the application for a patent for invention of optical glass, gas preform, optical element and optical instrument ".
Technical field
The present invention relates to a kind of optical glass, is 1.58~1.65, Abbe number more particularly to a kind of refractive index (nd) (vd) environmental protection optical glass for being 40~50, and prefabricated component, optical element and the optical instrument being made up of the optical glass.
Background technology
Contain the substantial amounts of PbO and As fining agent in traditional barium flint optical glass component2O3.With environment The increasingly strict of regulation is protected, the most countries regulation such as Europe, the U.S., China is except in military glass and non-browning glass In allow add PbO and As2O3In addition, other purposes glass can not contain the PbO and As harmful to human body and environment without exception2O3。 So major optical instrument manufacturer refusal uses and contains PbO and As2O3Optical glass.It is a kind of new that this requires that we develop Glass ingredient, requirement can be met, environmentally harmful material can not be contained again, while require low in raw material price, Being capable of a large amount of continuous production at low cost.
For refractive index between 1.58~1.65, unleaded barium flint optical glass of the Abbe number between 40~50 Glass, some optical constants are contained in this scope or the crown glass close with this scope in previous patent document.However, just At present from the point of view of optical glass production field low cost, quantity-produced requirement, these glass ingredients more or less lack in the presence of some Point.
CN101549955A discloses a kind of optical glass, wherein containing substantial amounts of PbO, it is impossible to meets that above-mentioned environmental protection will Ask.JP8048538A discloses a kind of optical glass, the Nb containing 6-35%2O5, the fluoride containing 0.1-10% simultaneously. Nb2O5It is a kind of very expensive raw material, so substantial amounts of Nb is added in this component2O5Cost of material will certainly be caused to rise. In addition, adding 0.1-10% fluoride, in actual production process, fluoride gas and dust can be discharged, increase environment is born Lotus and processing cost.
In optical glass disclosed in CN1207230C and CN1044223C, TiO2Content it is higher, CN1044223C components In contain up to 21-25.2% TiO2Although TiO2Addition can significantly lift refractive index and the dispersion of glass, but with TiO2Content increase, optical glass easily colours, and an important indicator light transmission rate of optical glass can significantly deteriorate.
The content of the invention
The technical problems to be solved by the invention are to provide one kind and do not contain expensive Nb2O5And Li2O, and pollution The PbO and As of environment2O3, while optical property meets that refractive index is 1.58~1.65, Abbe number is 40~50 environmentally friendly optics glass Glass.
The technical proposal for solving the technical problem of the invention is：Environmental protection optical glass, glass density 3.3g/cm3 Hereinafter, refractive index is 1.58~1.65, and Abbe number is 40~50, and transition temperature is less than 600 DEG C, when transmittance reaches 80% pair The wavelength X answered80Less than 390nm, transmittance reaches corresponding wavelength X when 5%5Less than 350nm；It is water-fast to act as 1 grade, acidproof work With for 1 grade, Nb is added without2O5、Li2O、PbO、As2O3And fluoride.
Further, composition is by weight percentage：SiO2：40~60%, B2O3：1~10%, BaO：12~32%, ZnO：1~8%, TiO2：2~12%, K2O：2~12%, Na2O:1~8%, CaO：0~8%, ZrO2：0~5%, Sb2O3：0 ~0.1%.
Further, NaO2With K2O total amount is 10~20%.
Further, SiO2：40~55%.
Further, B2O3：2~6%.
Further, BaO：15~30%.
Further, ZnO：2~5%.
Further, TiO2：5~10%.
Further, K2O：6~10%.
Further, Na2O：1~5%.
Further, CaO：0~5%.
Further, ZrO2：0~3%.
Environmental protection optical glass, by weight percentage composition are：SiO2：40~60%, B2O3：1~10%, BaO：12~ 32%th, ZnO：1~8%, TiO2：2~12%, K2O：2~12%, Na2O:1~8%, CaO：0~8%, ZrO2：0~5%, Sb2O3：0~0.1%.
Further, NaO2With K2O total amount is 10~20%.
Further, SiO2：40~55%.
Further, B2O3：2~6%.
Further, BaO：15~30%.
Further, ZnO：2~5%.
Further, TiO2：5~10%.
Further, K2O：6~10%.
Further, Na2O：1~5%.
Further, CaO：0~5%.
Further, ZrO2：0~3%.
Using gas preform made of above-mentioned environmental protection optical glass.
Using optical element made of above-mentioned environmental protection optical glass.
Using optical instrument made of above-mentioned environmental protection optical glass.
The beneficial effects of the invention are as follows：It is added without expensive Nb2O5、Li2O, production cost is reduced, saved money Source；Pass through Reasonable adjustment TiO2Component, make the light transmission rate of glass excellent；PbO, As are not contained2O3With the pollution group such as fluoride Point, the refractive index of obtained environmental protection optical glass is 1.58~1.65, and Abbe number is 40~50, and the transition temperature of glass is 600 Below DEG C, density 3.3g/cm3Hereinafter, transmittance reaches corresponding wavelength X when 80%80Less than 390nm, transmittance reaches 5% When corresponding wavelength X5Less than 350nm.
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 40%, the chemical stability of glass can reduce；But when its content is more than 60%, 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 40~60%, preferably 40~55%.
B2O3It is the component that must contain in the present invention, when its content is less than 1%, the melt characteristic of glass is bad, if When its content is higher than 10%, glass volatility when melting increases, while the devitrification characteristic of glass is deteriorated, therefore, B2O3Contain Amount is defined to 1~10%, preferably 2~6%.
BaO is the component that must contain in the present invention, can improve the refractive index and devitrification resistance property of glass.In the present invention In, when BaO content is less than 12%, it is impossible to reach required optical constant, if content is more than 32%, easily continuous Data are unstable in melting, can also aggravate corrosion production body of heater.Therefore, BaO contents be defined to 12~32%, preferably 15~ 30%.
TiO2It is used for refractive index and the dispersion for improving glass in the present invention, to reach required optical constant.Meanwhile TiO2The mechanical performance and chemical stability of glass can also be significantly increased.But if TiO2Content be less than 2%, then Glass can not reach desired optical constant, if content is higher than 12%, can cause the notable deterioration of light transmission rate.Therefore, TiO2Content is 2~12%, preferably 5~10%.
ZnO main function be adjust glass optical constant, while can also improve glass surface gloss and Reduce the softening temperature of glass.If ZnO content is less than 1%, improvement unobvious；If content more than 8%, can cause glass Cost of material dramatically increases.Therefore, ZnO content is 1~8%, preferably 2~5%.
Na2O can not only adjust the optical constant of glass, can also reduce the solution temperature and high temperature viscosity of glass, have Beneficial to exclusion that is energy-saving, while also helping Bubbles in Glass.In order to reach the effect of the present invention, Na2O content is 1 ~8%, preferably 1~5%.
K2O is one of component that the present invention must add, for adjusting optical constant and reducing the solution temperature of glass. When its content is less than 2%, the effect above is unable to reach；If content more than 12%, can cause the evil of chemical durability of glass Change.Therefore, K2O content is 2~12%, preferably 6~10%.
In addition, work as NaO2With K2When O total amount reaches more than 10%, the solution temperature and height of glass can be just significantly reduced Warm viscosity.But work as NaO2With K2When O total amount is more than 20%, then the chemical stability of glass can deteriorate.Therefore, NaO2With K2O Total amount be 10~20%.
CaO can improve stability, glass, melting sources can also be helped when melting produces, but its content is higher than 8% When, the tendency towards devitrification increase of glass, therefore CaO content is defined to 0~8%, preferably 0~5%.
ZrO2Viscosity, hardness, elasticity, refractive index and the chemical stability of optical glass can be improved, and glass can be reduced Thermal coefficient of expansion.Work as ZrO2Content more than 5% when, will appear from crystallization, and reduce the devitrification resistance of glass.Cause This, ZrO2Content be 0~5%, preferred content be 0~3%.
Sb2O3Used in the present invention as fining agent, its content range is 0~0.1%, is preferably added without.
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.
Transition temperature (Tg) according to《GB/T7962.16-1987 colouless optical glass method of testings linear expansion coefficient, transformation Temperature and sag 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.
Density according to《GB/T 7962.20-1987 colouless optical glass method of testing density measurement methods》Test.
Water-fast effect stability DW(powder method), test by GB/T17129 method of testings, calculated according to following formula：
DW=(B-C)/(B-A) * 100
In formula：DW- glass leaches percentage (%)
The quality (g) of B-filter and sample
The quality (g) of sample after C-filter and erosion
A-filter quality (g)
By the leaching percentage being calculated, by the stable D of the water-fast effect of optical glassWIt is divided into 6 classes see the table below.
Classification 1 2 3 4 5 6
Leach percentage (DW) ＜ 0.04 0.04-0.10 0.10-0.25 0.25-0.60 0.60-1.10 ＞ 1.10
Acidproof effect stability DA(powder method), tested by GB/T17129 method of testings.
Optical glass shortwave transmitted spectrum characteristic degree of staining (λ80/λ5) represent.I.e. thickness of sample is 10mm ± 0.1mm, λ80Refer to that glass transmittance reaches corresponding wavelength, λ when 80%5Refer to that glass transmittance reaches corresponding wavelength when 5%.
By test, optical glass of the invention has following performance：Density (ρ) is 3.3g/cm3Below；Refractive index (nd) 1.58~1.65；Abbe number (vd) is 40~50；Transition temperature (Tg) is less than 600 DEG C；When transmittance reaches 80% pair The wavelength X answered80Less than 390nm, transmittance reaches corresponding wavelength X when 5%5Less than 350nm；DWFor 1 grade；DAFor 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, and described optical element can apply 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 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 simultaneously by the ratio according to each embodiment shown in table 1~3 Hybrid optical glass is put mixed material with common raw material (such as oxide, hydroxide, carbonate, nitrate and fluoride) Put in platinum crucible, melted in certain temperature, and after melting, clarify, stirring and being homogenized, obtain no bubble And the homogeneous melt glass without undissolved material, 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), glass transformation temperature (Tg), water-fast effect stability (DW), acidproof effect stability (DA), degree of staining (λ80/λ5) the result table in table 1~3 together Show.In these tables, the composition of each component is represented with weight %.
Table 1
Table 2
Table 3
Glass of the present invention can be seen that by the embodiment in above-mentioned 1~table of table 3 and be added without expensive Nb2O5With Li2O, production cost is reduced, saved resource；Pass through Reasonable adjustment SiO2、TiO2Etc. component, make the light transmission rate of glass excellent It is different, without PbO, As2O3With the pollution components such as fluoride so that glass density (ρ) is 3.3g/cm3Hereinafter, refractive index (nd) is 1.58~1.65, Abbe number (vd) is 40~50, and transition temperature (Tg) is less than 600 DEG C, and transmittance reaches corresponding when 80% Wavelength X80Less than 390nm, transmittance reaches corresponding wavelength X when 5%5Less than 350nm；It is water-fast to act as 1 grade, it is acidproof to act as 1 grade.

Claims (13)

1. environmental protection optical glass, it is characterised in that glass density 3.3g/cm3Hereinafter, refractive index is 1.58~1.65, Abbe number For 40~50, transition temperature is less than 600 DEG C, and transmittance reaches corresponding wavelength X when 80%80Less than 390nm, transmittance reaches Corresponding wavelength X when 5%5Less than 350nm；It is water-fast to act as 1 grade, it is acidproof to act as 1 grade, it is added without Nb2O5、Li2O、PbO、 As2O3And fluoride.
2. environmental protection optical glass as claimed in claim 1, it is characterised in that it, which is formed, represents to contain by weight percentage： SiO2：40~60%, B2O3：1~10%, BaO：12~32%, ZnO：1~8%, TiO2：2~12%, K2O：2~12%, Na2O：1~8%.
3. environmental protection optical glass as claimed in claim 1 or 2, it is characterised in that its composition represents also to contain by weight percentage Have：CaO：0~8%, ZrO2：0~5%, Sb2O3：0~0.1%.
4. environmental protection optical glass, it is characterised in that composition is by weight percentage：SiO2：40~60%, B2O3：1~10%, BaO：12~32%, ZnO：1~8%, TiO2：2~12%, K2O：2~12%, Na2O：1~8%, CaO：0~8%, ZrO2：0 ~5%, Sb2O3：0~0.1%.
5. environmental protection optical glass, it is characterised in that it, which is formed, represents to contain by weight percentage：SiO2：40~60%, B2O3：1 ~10%, BaO：12~32%, ZnO：1~8%, TiO2：2~12%, K2O：2~12%, Na2O：1~8%, CaO：0~ 8%th, ZrO2：0~5%, Sb2O3：0~0.1%.
6. environmental protection optical glass as claimed in claim 5, it is characterised in that do not contain Nb2O5、Li2O、PbO、As2O3And fluorination Thing.
7. the environmental protection optical glass as described in claim 1~6 any claim, it is characterised in that wherein：SiO2：40~ 55%；And/or B2O3：2~6%；And/or BaO：15~30%；And/or ZnO：2~5%；And/or TiO2：5~10%；With/ Or K2O：6~10%；And/or Na2O：1~5%；And/or CaO：0~5%；And/or ZrO2：0~3%.
8. the environmental protection optical glass as described in claim 1~6 any claim, it is characterised in that NaO2With K2O's is total Measure as 10~20%.
9. the environmental protection optical glass as described in claim 4~6 any claim, it is characterised in that glass density 3.3g/ cm3Hereinafter, transition temperature is less than 600 DEG C, and transmittance reaches corresponding wavelength X when 80%80Less than 390nm, transmittance reaches Corresponding wavelength X when 5%5Less than 350nm；It is water-fast to act as 1 grade, it is acidproof to act as 1 grade.
10. the environmental protection optical glass as described in claim 4~6 any claim, it is characterised in that the refractive index of glass is 1.58~1.65, Abbe number is 40~50.
11. using gas preform made of the environmental protection optical glass described in any claim in claim 1~10.
12. using optical element made of the environmental protection optical glass described in any claim in claim 1~10.
13. using optical instrument made of the environmental protection optical glass described in any claim in claim 1~10.
CN201710874397.0A 2013-02-25 2013-02-25 Environmental protection optical glass, gas preform, optical element and optical instrument Pending CN107473584A (en)

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CN201710874397.0A CN107473584A (en) 2013-02-25 2013-02-25 Environmental protection optical glass, gas preform, optical element and optical instrument
CN201310058615.5A CN104003615A (en) 2013-02-25 2013-02-25 Environmentally friendly optical glass, glass preform, optical element and optical instrument

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN109205616A (en) * 2018-11-21 2019-01-15 成都光明光电股份有限公司 Optical glass, gas preform, optical element and optical instrument
CN109896740A (en) * 2019-04-24 2019-06-18 成都光明光电股份有限公司 Optical glass and optical element
CN111217519A (en) * 2018-11-27 2020-06-02 宜城市泳瑞玻璃科技有限公司 Environment-friendly optical glass

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Publication number Priority date Publication date Assignee Title
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
CN107098583B (en) * 2017-05-04 2019-10-29 湖北戈碧迦光电科技股份有限公司 A kind of optical glass
CN110550860A (en) * 2019-09-30 2019-12-10 成都光明光电股份有限公司 Optical glass

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109205616A (en) * 2018-11-21 2019-01-15 成都光明光电股份有限公司 Optical glass, gas preform, optical element and optical instrument
CN111217519A (en) * 2018-11-27 2020-06-02 宜城市泳瑞玻璃科技有限公司 Environment-friendly optical glass
CN109896740A (en) * 2019-04-24 2019-06-18 成都光明光电股份有限公司 Optical glass and optical element
CN109896740B (en) * 2019-04-24 2022-04-22 成都光明光电股份有限公司 Optical glass and optical element

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Application publication date: 20171215