CN109626814A - Environmental protection optical glass, optical precast product, optical element and optical instrument - Google Patents

Environmental protection optical glass, optical precast product, optical element and optical instrument Download PDF

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Publication number
CN109626814A
CN109626814A CN201910012401.1A CN201910012401A CN109626814A CN 109626814 A CN109626814 A CN 109626814A CN 201910012401 A CN201910012401 A CN 201910012401A CN 109626814 A CN109626814 A CN 109626814A
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environmental protection
optical glass
bao
zno
glass
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CN109626814B (en
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袁伟
赖德光
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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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    • 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
    • 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
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • 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
    • 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
    • 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
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • 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
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • 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
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • 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
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • 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)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Ceramic Engineering (AREA)
  • Glass Compositions (AREA)

Abstract

The present invention provides a kind of environmental protection optical glass, and component indicates by weight percentage, contains: SiO2: 30~50%, TiO2: 2~20%, ZnO:15~35%, ZrO2: 0~10%, BaO:5~24%, Na2O:0~15%, K2O:0~10%, wherein ZnO/BaO is 0.8~5.0.It is designed by reasonable component, in the case where obtaining the optical properties such as desired refractive index and Abbe number, there is excellent chemical stability.

Description

Environmental protection optical glass, optical precast product, optical element and optical instrument
Technical field
The present invention relates to a kind of optical glass, more particularly, to a kind of environmental protection optical glass, optical precast product, optical element And optical instrument.
Background technique
With continuous the merging of optics and electronic information science, new material science, the optics as photoelectron basic material Glass is advanced by leaps and bounds in the application of the technical fields such as optical transport, light storage and photoelectric display.In recent years, optical element and optics instrument Device is quickly grown in terms of digitlization, integrated and High precision, this is in the optical element for optical instrument and equipment Optical glass performance more stringent requirements are proposed.
Optical glass is possible to will receive the erosion of environment and various chemical reagent and medical fluid, therefore light in use The resistivity that glass corrodes these is learned, i.e. the chemical stability of optical glass extremely closes the service precision of instrument and service life It is important.Meanwhile as the cry of environmental protection in the world is higher and higher, unleaded and without arsenic the research and development of optical glass Operation duration carry out in, in the optical glass as disclosed in CN101549955A containing 20~60% lead oxide, be not obviously inconsistent Cyclization guaranteed request.
Summary of the invention
Based on the above reasons, technical problem to be solved by the invention is to provide a kind of rings with superior chemical stability Protect optical glass and optical precast product, optical element and optical instrument.
The technical proposal for solving the technical problem of the invention is:
(1) environmental protection optical glass, component indicate by weight percentage, contain: SiO2: 30~50%, TiO2: 2~ 20%, ZnO:15~35%, ZrO2: 0~10%, BaO:5~24%, Na2O:0~15%, K2O:0~10%, wherein ZnO/ BaO is 0.8~5.0.
(2) environmental protection optical glass, component indicate by weight percentage, contain: SiO2: 30~50%, TiO2: 2~ 20%, ZnO:15~35%, ZrO2: 0~10%, BaO:5~24%, Na2O:0~15%, K2O:0~10%.
(3) according to (1) or (2) any environmental protection optical glass, component indicates by weight percentage, also contains: Li2O:0~10%, Nb2O5: 0~8%, Ln2O3: 0~10%, B2O3: 0~10%, CaO:0~8%, SrO:0~8%, MgO: 0~8%, Al2O3: 0~8%, WO3: 0~8%, clarifying agent: 0~1%, wherein Ln2O3For La2O3、Gd2O3、Y2O3And Yb2O3In One or more, clarifying agent Sb2O3、SnO2, SnO and CeO2One of or it is a variety of.
(4) environmental protection optical glass, component indicate by weight percentage, by SiO2: 30~50%, TiO2: 2~20%, ZnO:15~35%, ZrO2: 0~10%, BaO:5~24%, Na2O:0~15%, K2O:0~10%, Li2O:0~10%, Nb2O5: 0~8%, Ln2O3: 0~10%, B2O3: 0~10%, CaO:0~8%, SrO:0~8%, MgO:0~8%, Al2O3: 0 ~8%, WO3: 0~8%, clarifying agent: 0~1% composition, wherein ZnO/BaO is 0.8~5.0, Ln2O3For La2O3、Gd2O3、Y2O3 And Yb2O3One of or a variety of, clarifying agent Sb2O3、SnO2, SnO and CeO2One of or it is a variety of.
(5) environmental protection optical glass contains SiO2、TiO2, ZnO, alkali metal oxide and alkaline earth oxide, the ring The refractive index (nd) for protecting optical glass is 1.64~1.71, Abbe number (νd) be 35~40, crystallization ceiling temperature be 1150 DEG C with Under, the alkali metal oxide is Na2O、K2O and Li2One of O or a variety of, the alkaline earth oxide be MgO, CaO, One of SrO and BaO or a variety of.
(6) according to any environmental protection optical glass in (1)~(5), in which: SiO2: 35~50%, and/or TiO2: 5~ 15%, and/or ZnO:18~30%, and/or ZrO2: 0.5~8%, and/or BaO:8~22%, and/or Na2O:3~12%, And/or K2O:0.5~8%, and/or Li2O:0~5%, and/or Nb2O5: 0~5%, and/or Ln2O3: 0~5%, and/or B2O3: 0~5%, and/or CaO:0~5%, and/or SrO:0~5%, and/or MgO:0~5%, and/or Al2O3: 0~5%, And/or WO3: 0~5%, and/or clarifying agent: 0~0.5%, wherein Ln2O3For La2O3、Gd2O3、Y2O3And Yb2O3One of Or a variety of, clarifying agent Sb2O3、SnO2, SnO and CeO2One of or it is a variety of.
(7) according to any environmental protection optical glass in (1)~(6), in which: SiO2: 35~45%, and/or TiO2: 7~ 13%, and/or ZnO:20~28%, and/or ZrO2: 1~5%, and/or BaO:10~18%, and/or Na2O:5~10%, And/or K2O:1~5%, and/or Li2O:0~2%, and/or Nb2O5: 0~2%, and/or Ln2O3: 0~3%, and/or B2O3: 0 ~2%, and/or CaO:0~2%, and/or SrO:0~2%, and/or MgO:0~2%, and/or Al2O3: 0~2%, and/or WO3: 0~3%, and/or Sb2O3: 0~0.5%, wherein Ln2O3For La2O3、Gd2O3、Y2O3And Yb2O3One of or it is a variety of.
(8) according to any environmental protection optical glass in (1)~(7), in which: ZnO/BaO is 1.0~3.0, preferably ZnO/ BaO is 1.2~2.5.
(9) according to any environmental protection optical glass in (1)~(8), in which: TiO2/SiO2It is 0.15~0.5, preferably TiO2/SiO2It is 0.15~0.4, more preferable TiO2/SiO2It is 0.2~0.35.
(10) according to any environmental protection optical glass in (1)~(9), in which: Nb2O5The value of/ZnO is 0.4 hereinafter, excellent Select Nb2O5The value of/ZnO is 0.2 hereinafter, more preferable Nb2O5The value of/ZnO is below 0.1.
(11) according to any environmental protection optical glass in (1)~(10), in which: K2O/(Li2O+Na2O+K2O value) is 0.1~0.45, preferably K2O/(Li2O+Na2O+K2O value) is 0.12~0.4, more preferable K2O/(Li2O+Na2O+K2O value) is 0.15~0.35.
(12) according to any environmental protection optical glass in (1)~(11), in which: (Na2O+K2O)/BaO is 0.2~2.0, It is preferred that (Na2O+K2O)/BaO is 0.3~1.5, more preferable (Na2O+K2O)/BaO is 0.4~1.0.
(13) according to any environmental protection optical glass in (1)~(12), in which: (SiO2+ZrO2)/(ZnO+TiO2) be 0.55~3.0, preferably (SiO2+ZrO2)/(ZnO+TiO2) in 0.7~2.5, more preferably (SiO2+ZrO2)/(ZnO+TiO2) be 0.8~1.8.
(14) according to any environmental protection optical glass in (1)~(13), in which: BaO/ (MgO+CaO+SrO+BaO) is 0.7~1.0, preferably BaO/ (MgO+CaO+SrO+BaO) are 0.8~1.0, and more preferable BaO/ (MgO+CaO+SrO+BaO) is 0.9 ~1.0.
(15) according to any environmental protection optical glass in (1)~(14), in which: (Li2O+ZnO)/SiO2For 0.35~ 1.2, preferably (Li2O+ZnO)/SiO2It is 0.4~1.0, more preferable (Li2O+ZnO)/SiO2It is 0.45~0.85.
(16) according to any environmental protection optical glass in (1)~(15), the refractive index (nd) of the environmental protection optical glass It is 1.64~1.71, preferably 1.65~1.70, more preferably 1.66~1.69；Abbe number (νd) it is 35~40, preferably 36 ~40, more preferably 36~39.
(17) according to any environmental protection optical glass in (1)~(16), the water-fast effect of the environmental protection optical glass is steady Qualitative (DW) it is 2 classes or more, preferably 1 class；And/or acidproof effect stability (DA) it is 2 classes or more, preferably 1 class.
(18) according to any environmental protection optical glass in (1)~(17), the bubble degree of the environmental protection optical glass is B grades More than, preferably A grades or more, more preferably A0Grade or more；And/or striped degree is C grades or more, preferably B grades or more.
(19) according to any environmental protection optical glass in (1)~(18), the thermal expansion coefficient of the environmental protection optical glass (α20~120 DEG C) it is 85 × 10-7/ K is hereinafter, preferably 80 × 10-7/ K is hereinafter, more preferably 78 × 10-7/ K or less；And/or crystallization Ceiling temperature is for 1150 DEG C hereinafter, preferably 1100 DEG C hereinafter, more preferably 1050 DEG C or less；And/or transition temperature (Tg) be 600 DEG C hereinafter, preferably 590 DEG C hereinafter, more preferably 585 DEG C or less.
(20) optical precast product is made of any environmental protection optical glass in (1)~(19).
(21) optical element is made of any environmental protection optical glass in (1)~(19), or using light described in 20 Prefabricated component is learned to be made.
(22) optical instrument containing any environmental protection optical glass in (1)~(19), or contains the member of optics described in 21 Part.
The beneficial effects of the present invention are: the present invention is designed by reasonable component, desired refractive index and Abbe are being obtained In the case where the optical properties such as number, there is excellent chemical stability.
Specific embodiment
In the following, the embodiment of environmental protection optical glass of the invention is described in detail, but the present invention is not limited to following Embodiment, can be carried out in the range of the object of the invention it is appropriate change to be implemented.In addition, about repeated explanation portion Point, although there is the case where omitting the description appropriate, but not therefore limit the purport invented.Sometimes it incite somebody to action this in the following contents Invention environmental protection optical glass is referred to as optical glass or glass.
[optical glass]
The each component range of optical glass of the present invention is illustrated below.In the present specification, if without special theory Bright, the content of each component is all using the weight percent table of the glass substance total amount relative to the composition for being converted into oxide Show.Herein, described " composition for being converted into oxide " refers to, as optical glass constituent of the invention raw material and make In the case that oxide, complex salt and hydroxide etc. decompose when melting and are changed into oxide, by the object of the oxide Matter total amount is as 100%.
Unless in particular situations it is further noted that numberical range listed herein includes upper and lower bound value, " more than " " following " includes endpoint value, and including all integers and score in the range, and is not limited to limited range when institute The occurrence of column.Herein referred "and/or" is inclusive, such as " A and/or B ", refers to only A, or only B, Huo Zhetong When have A and B.
<necessary component and optional components>
SiO2It is the necessary component of optical glass of the present invention, is the skeleton of optical glass of the present invention.By by SiO2Content Design can be improved the acid resistance and viscosity of glass, reduce the abrasion degree of glass 30% or more.Therefore, SiO in the present invention2 Content lower limit be 30%, preferred lower limit 35%.But work as SiO2Content when being more than 50%, the meltdown property of glass is sharply It is deteriorated, the coloring of glass is easy to cause to increase.Therefore, SiO in the present invention2The upper limit of content be 50%, preferred upper limit is 45%.
TiO2Performance with high-refraction high-dispersion is added in optical glass of the present invention and the refractive index of glass can be improved. Pass through the TiO of 2% or more introducing in the present invention2, the devitrification resistance energy and chemical stability of glass can be improved.Therefore the present invention TiO in optical glass2Lower limit be 2%, preferred lower limit 5%, more preferable lower limit be 7%.On the other hand, by controlling TiO2 20% hereinafter, the coloring of glass can be reduced, the transmitance of glass shortwave wavelength is improved.In some embodiments, pass through Control TiO215% hereinafter, the partial dispersion ratio of glass can be made to be not easy to rise, the readily available glass with lower part dispersion ratio Glass.Therefore, TiO in optical glass of the present invention2The upper limit be 20%, preferred upper limit 15%, the more preferable upper limit be 13%.
In certain embodiments of the present invention, by controlling TiO2And SiO2Content ratio TiO2/SiO2Range be 0.15~0.5, the devitrification resistance energy of glass can be improved, be easy to get desired optical constant and chemical stability, further , preferably make TiO2/SiO2Range also contribute to the meltbility of glass 0.15~0.4, and improve the light of glass Transmitance, more preferable TiO2/SiO2Range be 0.2~0.35.
ZrO2Belong to high refractive index oxide, the refractive index of glass can be improved, while improving the chemical stability of glass；This In invention, by containing 10% ZrO below2It is also improved the extremely dispersed effect of glass, the exception of glass is dispersed to be had Conducive to eliminating second order spectrum, therefore ZrO in optical glass of the present invention in optical design2Content be 10% or less.In some realities It applies in mode, ZrO2Content be lower than 0.5%, foregoing advantages are unobvious, but additional amount is more than 8%, then can improve the analysis of glass Brilliant risk.Therefore, ZrO2Content be preferably 0.5~8%, more preferably 1~5%.
Nb2O5It is high-refraction high-dispersion component, is the optional components in the present invention, passes through control Nb in the present invention2O5Contain It measures 8% hereinafter, the reduction of glass devitrification resistance can be inhibited, and is easy to get the glass with desired dispersion.Therefore, Nb in optical glass of the present invention2O5Content be 8% hereinafter, preferably 5% hereinafter, more preferably 2% or less.In some implementations In mode, by not containing Nb2O5, the transmitance and devitrification resistance energy of glass can be improved.
ZnO is the necessary component that the melting temperature of glass transition temperature and glass raw material is reduced in the present invention.In the present invention By the ZnO containing 15% or more, the chemical stability of glass can be improved, improve the meltability of raw material, promote glass blister Discharge, reduces the high temperature viscosity of glass；But when ZnO content is higher than 35%, the devitrification resistance of glass can deteriorate, and due to viscosity mistake It is low and be easy to cause devitrification.Therefore in optical glass of the present invention, the content of ZnO is 15~35%, preferably 18~30%, more excellent It is selected as 20~28%.
In certain embodiments of the present invention, by controlling Nb2O5The value of/ZnO is 0.4 hereinafter, can improve glass Viscosity, and optical glass is made to obtain excellent bubble degree, especially Nb2O5The value of/ZnO is 0.2 hereinafter, optical glass can be improved Chemical stability, and the bubble degree of optical glass is made to reach A grades or more, more preferable Nb2O5The value of/ZnO is below 0.1.
Inventors discovered through research that in certain embodiments of the present invention, by making (SiO2+ZrO2)/(ZnO+ TiO2) in 0.55~3.0 range, optical glass can be made to obtain excellent chemical stability and at glass stability；Further Make (SiO2+ZrO2)/(ZnO+TiO2) in 0.7~2.5 range, it can also optimize the bubble degree of optical glass, more preferable (SiO2+ ZrO2)/(ZnO+TiO2) it is 0.8~1.8.
BaO can be improved the devitrification resistance of glass, adjust the thermal expansion coefficient of glass.Particularly, pass through introducing in the present invention 5% or more BaO can make optical glass of the present invention obtain desired optical constant and chemical stability, and therefore, BaO's contains Measuring lower limit is 5%, preferred lower limit 8%, and more preferable lower limit is 10%.On the other hand, by make BaO content 24% hereinafter, The luminous transmittance of glass can be improved, and keep the glass in melting more stable.Therefore the upper content limit of BaO is 24%, preferred upper limit It is 22%, the more preferable upper limit is 18%.
It is found by inventor's lot of experiments, it, can to make optical glass of the present invention obtain excellent chemical stability By making the range of ZnO/BaO in 0.8~5.0；Further, when the value of ZnO/BaO is more than 3.0, the anti-analysis of glass Brilliant performance decline, when the value of ZnO/BaO is less than 1.0, the transition temperature and thermal expansion coefficient of glass rise, therefore light of the present invention In some embodiments for learning glass, preferably the range of ZnO/BaO is 1.0~3.0；Further, by controlling ZnO/BaO Range be 1.2~2.5, so that optical glass of the present invention is obtained excellent striped degree.
CaO is the component for improving glass devitrification resistance, reducing glass abrasion degree, is the optional components in glass of the present invention. By making the content 8% of CaO hereinafter, glass refraction can be inhibited while improving the devitrification resistance of glass in the present invention The reduction of rate.Therefore the upper content limit of CaO is 8% in the present invention, preferred upper limit 5%, and the more preferable upper limit is 2%.
SrO can effectively adjust the optical constant of glass, but its content is excessive, then the devitrification resistance ability decline of glass.This The upper content limit that SrO is controlled in invention is 8%, and preferred upper limit 5%, the more preferable upper limit is 2%.
The optical constant of the adjustable glass of MgO, improves the chemical stability of glass, is the optional of optical glass of the present invention Component.By containing 8% MgO below in the present invention, the meltbility of glass can be improved.Therefore in the present invention in the content of MgO It is limited to 8%, preferred upper limit 5%, the more preferable upper limit is 2%.
MgO, CaO, SrO and BaO are alkaline earth oxides, but the effect in optical glass of the present invention is different, because This not can arbitrarily be replaced mutually.Find that MgO, CaO, SrO and BaO are in glass system by inventor's lot of experiments In content ratio, the performance of optical glass is had a major impact；Further, the range of BaO/ (MgO+CaO+SrO+BaO) At 0.7~1.0, optical glass can be made to obtain excellent thermal expansion coefficient and striped degree, preferably BaO/ (MgO+CaO+SrO+ BaO range) is 0.8~1.0, and the range of more preferable BaO/ (MgO+CaO+SrO+BaO) is 0.9~1.0.
Na2O is the component for improving glass melting.In the present invention, by making Na2The content of O is 15% hereinafter, can change Reduce the thermal expansion coefficient of glass while good chemical durability of glass.In some embodiments, it is preferred making Na2O content is 3 In~12% range, also optimizes the formability of glass, improves light transmission.Therefore in optical glass of the present invention, Na2O content 15% is limited to hereinafter, preferably 3~12%, more preferably 5~10%.
K2O can reduce the transition temperature of glass, but its content is higher than 10%, then the devitrification resistance decline of glass.One In a little embodiments, it is preferably introduced into 0.5~8% K2O can make glass obtain excellent water-fast effect stability.Therefore originally K in invention2O content is limited to 10% hereinafter, preferably 0.5~8%, and more preferably 1~5%.
Li2O can reduce the transition temperature of glass, but its content is higher than 10%, then under the acidproof effect stability of glass Drop, therefore, Li in the present invention2The content of O controls below 10%.In some embodiments, by controlling Li2The content of O exists 5% hereinafter, can be improved the viscosity of glass, improve the striped degree of glass.Therefore, Li2The content of O is preferably 5% hereinafter, more excellent It is selected as 2% or less.
Although Li2O、Na2O and K2O is alkali metal oxide, but the effect in optical glass of the present invention is different, By adjusting its content in optical glass respectively, the performance of optical glass can be advanced optimized.In some realities of the invention It applies in mode, by making K2O/(Li2O+Na2O+K2O the anti-crystallization of optical glass can be improved in 0.1~0.45 range in value) Performance especially makes K2O/(Li2O+Na2O+K2O the striped degree of glass also can be improved in 0.12~0.4 range in value), into The preferred K of one step2O/(Li2O+Na2O+K2O value) is 0.15~0.35.In some embodiments, by making Na2The content > of O Li2The content of O, preferably Na2The content > K of O2The content > Li of O2The content of O, can be improved optical glass devitrification resistance can and Chemical stability.
In some embodiments, as (Li2O+ZnO)/SiO2When greater than 1.2, the devitrification resistance of optical glass can decline, As (Li2O+ZnO)/SiO2When less than 0.35, the transition temperature of optical glass is increased, therefore (Li in the present invention2O+ZnO)/SiO2 Range be 0.35~1.2；Through further research, it has been found that making (Li2O+ZnO)/SiO2In 0.4~1.0 range, light can be made It learns glass and obtains excellent bubble degree, further preferred (Li2O+ZnO)/SiO2It is 0.45~0.85.
In some embodiments, as (Na2O+K2O)/BaO value is higher than 2.0, the thermal expansion coefficient rising of glass, striped Degree reduces, as (Na2O+K2O)/BaO value is lower than 0.2, and the density of glass rises, therefore in optical glass of the present invention preferably (Na2O+K2O)/BaO value is 0.2~2.0, more preferably 0.3~1.5, further preferably 0.4~1.0.
B2O3Have the function of improving thermal stability and meltbility, but when its content is higher than 10%, the chemistry of glass Stability and devitrification resistance decline.B in the present invention2O3The upper limit be 10%, preferred upper limit 5%, the more preferable upper limit be 2%.? In some embodiments, by not introducing B2O3, can get desired chemical stability.
Al2O3The chemical stability of glass can be improved, but its content is excessive, the devitrification resistance and meltbility of glass reduce, Therefore its content is for 8% hereinafter, preferably 5% hereinafter, more preferably 3% or less.
WO3It is the optical constant of adjustable glass and the optional components of devitrification resistance, but when its content is more than 8%, glass The transmitance and devitrification resistance of glass can decline, therefore, WO3Upper content limit be 8%, preferably 5%, more preferably 3%, into one Step does not contain preferably.
Ln2O3It is the component for improving glass refraction and improving chemical durability of glass, is appointing in optical glass of the present invention Component is selected, wherein Ln2O3For La2O3、Gd2O3、Y2O3、Yb2O3One of or it is a variety of.By by Ln2O3Content control be 10% or less can be improved the devitrification resistance property of glass.Therefore, in optical glass of the invention, Ln2O3The upper limit of content range Value is 10%, preferred upper limit 5%, and the more preferable upper limit is 3%.
By the Sb for being added 0~1%2O3、SnO2, SnO and CeO2One of or various ingredients as clarifying agent, can be with The clarifying effect for improving glass, is preferably added to 0~0.5% clarifying agent.But work as Sb2O3When content is more than 1%, glass has clarification The tendency of reduced performance, simultaneously because its strong oxidation promotes the deterioration of molding die, therefore Sb of the present invention2O3Addition Amount is for 1% hereinafter, preferably 0.5% or less.SnO2, SnO can also be used as clarifying agent to add, but when its content is more than 1% When, glass can colour, or when heat, soften glass and carry out die forming etc. shape again when, Sn can become nucleus and generate Starting point, generate the tendency of devitrification, therefore SnO of the invention2With the difference content of SnO be 1% hereinafter, preferably 0.5% with Under, it does not contain further preferably.CeO2Effect and additive amount ratio and SnO2Unanimously, content is 1% hereinafter, preferably 0.5% hereinafter, do not contain further preferably.
In the range of not damaging glass performance of the invention, above-mentioned other groups not referred to can be added as needed Point, such as P2O5、GeO2、TeO2、Bi2O3、Ta2O5And Ga2O3Etc. components, but individually or mixing the content containing the above component on It is limited to 5%, preferred upper limit 3%, the more preferable upper limit is 1%.
<component that should not contain>
In glass of the present invention, the oxide of the transition metal such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo, even if individually Or in the case that compound ground contains on a small quantity, glass is also subject to coloration, the specific wavelength in visible light region generates absorption, thus The property for weakening raising visible light transmittance effect of the invention, therefore it is desirable, especially for the transmitance of visible light region wavelength The optical glass required, does not preferably contain actually.
The oxide of Th, Cd, Tl, Os, Be and Se have what control used to incline as harmful chemical substance in recent years To being to the measure of environmental protection in the manufacturing process of glass, the disposition after manufacturing procedure and commercialization not only must It needs.Therefore, it in the case where paying attention to the influence to environment, other than being inevitably mixed into, does not preferably contain actually They.Optical glass becomes the substance for not including pollution environment actually as a result,.Therefore, even if not taking special environment pair Measure in plan, optical glass of the invention are also able to carry out manufacture, processing and discard.
Environmental-friendly in order to realize, optical glass of the invention does not contain As2O3And PbO.Although As2O3With elimination gas Bubble and the effect for preferably preventing glass coloration, but As2O3Addition can increase glass smelting furnace is especially to the platinum of platinum smelting furnace Gold corrodes, and causes more platinum ions to enter glass, adversely affects to the service life of platinum smelting furnace.PbO can be significant The high refractive index of raising glass and high dispersion, but PbO and As2O3All cause the substance of environmental pollution.
" not introducing " " not containing " " 0% " described herein refers to not deliberately by the compound, molecule or element etc. It is added in optical glass of the present invention as raw material；But as the raw material and/or equipment of production optical glass, can exist certain It is not the impurity deliberately added or component, a small amount of or trace can contains in final optical glass, such situation is also in this hair In the protection scope of bright patent.
In the following, being illustrated to the performance of optical glass of the invention.
<refractive index and Abbe number>
Optical glass refractive index (nd) and Abbe number (νd) tested according to method as defined in GB/T 7962.1-2010.
The refractive index (nd) of optical glass of the present invention is 1.64~1.71, preferably 1.65~1.70, more preferably 1.66 ~1.69；Abbe number (νd) it is 35~40, preferably 36~40, more preferably 36~39.
<acidproof effect stability>
The acidproof effect stability (D of optical glassA) (powder method) according to method as defined in GB/T 17129 test.
The acidproof effect stability (D of optical glass of the present inventionA) it is 2 classes or more, preferably 1 class.
<water-fast effect stability>
Optical glass is water-fast effect stability (DW) (powder method) according to method as defined in GB/T 17129 test.
The water-fast effect stability (D of optical glass of the present inventionW) it is 2 classes or more, preferably 1 class.
<bubble degree>
The bubble degree of optical glass is by the test of method as defined in GB/T7962.8-2010.
Optical glass bubble degree of the present invention is B grades or more, preferably A grades or more, more preferably A0Grade or more.
<striped degree>
The striped degree of optical glass is measured by method as defined in MLL-G-174B.Method is with point light source and lens group At schlieren instrument, from the direction for being easiest to see striped, and standard sample audit by comparison is divided into 4 grades, respectively A, B, C, D grades, the A grades of stripeds to be visible by naked eyes under regulation testing conditions, B grades are to have striped that is thin and dispersing, C under regulation testing conditions Grade is to have slight parallel stripes under regulation testing conditions, and D grades are to have rough striped under regulation testing conditions.
The striped degree of optical glass of the invention is C grades or more, preferably B grades or more.
<crystallization ceiling temperature>
Using the crystallization property of temperature gradient furnace method measurement glass, glass is made to the sample of 180*10*10mm, side polishes, It is put into the furnace with temperature gradient (5 DEG C/cm) to take out after being warming up to 1400 DEG C of heat preservations 4 hours and naturally cools to room temperature, aobvious There is the crystallization ceiling temperature that the corresponding maximum temperature of crystal is glass in micro- microscopic observation devitrification of glass situation, glass.
The crystallization ceiling temperature of optical glass of the invention is for 1150 DEG C hereinafter, preferably 1100 DEG C hereinafter, more preferably 1050 DEG C or less.
<thermal expansion coefficient>
Thermal expansion coefficient (α20~120DEG C) tested according to method as defined in GB/T7962.16-2010.
Thermal expansion coefficient (the α of optical glass of the invention20~120 DEG C) it is 85 × 10-7/ K is hereinafter, preferably 80 × 10-7/K Hereinafter, more preferably 78 × 10-7/ K or less.
<transition temperature>
Transition temperature (the T of glassg) tested by method as defined in GB/T7962.16-2010.
Transition temperature (the T of optical glass of the inventiong) be 600 DEG C hereinafter, preferably 590 DEG C hereinafter, more preferably 585 DEG C or less.
<density>
Density (ρ) is tested according to method as defined in GB/T7962.20-2010.
The density (ρ) of optical glass of the invention is 3.8g/cm3Hereinafter, preferably 3.7g/cm3Hereinafter, more preferably 3.6g/cm3Hereinafter, further preferably 3.5g/cm3Below.
[manufacturing method]
The manufacturing method of optical glass of the present invention is as follows: glass of the invention is produced using conventional raw material and common process, The use of carbonate, nitrate, sulfate, oxide etc. is raw material, according to a conventional method after ingredient, the furnace charge prepared is put into It is melted in 1350~1400 DEG C of smelting furnace, after clarified and abundant homogenizing, in 1150~1200 DEG C of casting or leakage injection forming, i.e., It can get optical glass of the invention.Those skilled in the art can properly select raw material, process according to actual needs And technological parameter.
[optical precast product and optical element]
Molded such as the means of attrition process or reheating, compression molding precise punch forming means can be used, Optical precast product is made by made optical glass.I.e., it is possible to mechanical by being ground and being ground to optical glass etc. Processing makes optical precast product, or by the preform for making compression molding by optical glass, to the preform Carry out carrying out attrition process again after reheating is molded to make optical precast product, or and to attrition process is carried out it is manufactured pre- Precise punch forming is carried out at parison to make optical precast product.
It should be noted that the means for preparing optical precast product are not limited to above-mentioned means.As described above, optics of the invention Glass is useful for various optical elements and optical design, wherein particularly preferably by optical glass of the invention formed it is pre- at Parison carries out molded, precise punch forming of reheating etc., the optical elements such as production lens, prism using the preform.
Optical precast product and optical element of the invention is formed by the optical glass of aforementioned present invention.Optics of the invention Prefabricated component has excellent characteristics possessed by optical glass；Optical element of the invention has excellent spy possessed by optical glass Property, it is capable of providing the optical elements such as the costly various lens of optics, prism.
As the example of lens, can enumerate lens face be spherical surface or aspherical recessed meniscus shaped lens, male bend moon-shaped lens, The various lens such as biconvex lens, biconcave lens, plano-convex lens, plano-concave lens.
[optical instrument]
Optical glass of the present invention is formed by optical element and can make such as camera installation, picture pick-up device, display equipment and prison Control the optical instruments such as equipment.
Embodiment
<optical glass embodiment>
In order to further clearly illustrate and illustrate technical solution of the present invention, non-limiting embodiment below is provided.
The present embodiment obtains the optics glass with composition shown in 1~table of table 2 using the manufacturing method of above-mentioned optical glass Glass.In addition, the test method measures the characteristic of each glass through the invention, and measurement result is indicated in 1~table of table 2 In.
Table 1
Table 2
<optical precast product embodiment>
The means of the obtained glass of optical glass Examples 1 to 20 use such as attrition process or reheating are molded, The means of the compression moldings such as precise punch forming, it is saturating to make recessed meniscus shaped lens, male bend moon-shaped lens, biconvex lens, concave-concave The prefabricated component of the various lens such as mirror, plano-convex lens, plano-concave lens, prism etc..
<optical element embodiment>
By obtained these prefabricated components annealing of above-mentioned optical precast product embodiment, the same of the deformation of inside glass is being reduced When be finely adjusted so that the optical characteristics such as refractive index reach desirable value.
Then, each prefabricated component is ground, ground, make recessed meniscus shaped lens, male bend moon-shaped lens, biconvex lens, The various lens such as biconcave lens, plano-convex lens, plano-concave lens, prism.It can also Tu Bufang on the surface of obtained optical element Reflectance coating.
<optical instrument embodiment>
By optical element made from above-mentioned optical element embodiment by optical design, by using one or more optics Element forms optical component or optical module, can be used for such as imaging device, sensor, microscope, medical science, number and throws Shadow, communication, optical communication technique/information transmission, optics/illumination in automotive field, photoetching technique, excimer laser, crystalline substance Piece, computer chip and integrated circuit and electronic device including such circuit and chip, or taking the photograph for automotive field As equipment and device.

Claims (20)

1. environmental protection optical glass, which is characterized in that its component indicates by weight percentage, contains: SiO2: 30~50%, TiO2: 2 ~20%, ZnO:15~35%, ZrO2: 0~10%, BaO:5~24%, Na2O:0~15%, K2O:0~10%, wherein ZnO/ BaO is 0.8~5.0.
2. environmental protection optical glass according to claim 1, which is characterized in that its component indicates by weight percentage, also contains Have: Li2O:0~10%, Nb2O5: 0~8%, Ln2O3: 0~10%, B2O3: 0~10%, CaO:0~8%, SrO:0~8%, MgO:0~8%, Al2O3: 0~8%, WO3: 0~8%, clarifying agent: 0~1%, wherein Ln2O3For La2O3、Gd2O3、Y2O3With Yb2O3One of or a variety of, clarifying agent Sb2O3、SnO2, SnO and CeO2One of or it is a variety of.
3. environmental protection optical glass, which is characterized in that its component indicates by weight percentage, by SiO2: 30~50%, TiO2: 2~ 20%, ZnO:15~35%, ZrO2: 0~10%, BaO:5~24%, Na2O:0~15%, K2O:0~10%, Li2O:0~ 10%, Nb2O5: 0~8%, Ln2O3: 0~10%, B2O3: 0~10%, CaO:0~8%, SrO:0~8%, MgO:0~8%, Al2O3: 0~8%, WO3: 0~8%, clarifying agent: 0~1% composition, wherein ZnO/BaO is 0.8~5.0, Ln2O3For La2O3、 Gd2O3、Y2O3And Yb2O3One of or a variety of, clarifying agent Sb2O3、SnO2, SnO and CeO2One of or it is a variety of.
4. environmental protection optical glass described in any claim according to claim 1~3, which is characterized in that wherein: SiO2: 35~ 50%, and/or TiO2: 5~15%, and/or ZnO:18~30%, and/or ZrO2: 0.5~8%, and/or BaO:8~22%, And/or Na2O:3~12%, and/or K2O:0.5~8%, and/or Li2O:0~5%, and/or Nb2O5: 0~5%, and/or Ln2O3: 0~5%, and/or B2O3: 0~5%, and/or CaO:0~5%, and/or SrO:0~5%, and/or MgO:0~5%, And/or Al2O3: 0~5%, and/or WO3: 0~5%, and/or clarifying agent: 0~0.5%, wherein Ln2O3For La2O3、Gd2O3、 Y2O3And Yb2O3One of or a variety of, clarifying agent Sb2O3、SnO2, SnO and CeO2One of or it is a variety of.
5. environmental protection optical glass described in any claim according to claim 1~3, which is characterized in that wherein: SiO2: 35~ 45%, and/or TiO2: 7~13%, and/or ZnO:20~28%, and/or ZrO2: 1~5%, and/or BaO:10~18%, And/or Na2O:5~10%, and/or K2O:1~5%, and/or Li2O:0~2%, and/or Nb2O5: 0~2%, and/or Ln2O3: 0~3%, and/or B2O3: 0~2%, and/or CaO:0~2%, and/or SrO:0~2%, and/or MgO:0~2%, And/or Al2O3: 0~2%, and/or WO3: 0~3%, and/or Sb2O3: 0~0.5%, wherein Ln2O3For La2O3、Gd2O3、 Y2O3And Yb2O3One of or it is a variety of.
6. environmental protection optical glass described in any claim according to claim 1~3, which is characterized in that wherein: ZnO/BaO It is 1.0~3.0, preferably ZnO/BaO is 1.2~2.5.
7. environmental protection optical glass described in any claim according to claim 1~3, which is characterized in that wherein: TiO2/SiO2 It is 0.15~0.5, preferably TiO2/SiO2It is 0.15~0.4, more preferable TiO2/SiO2It is 0.2~0.35.
8. environmental protection optical glass described in any claim according to claim 1~3, which is characterized in that wherein: Nb2O5/ZnO Value 0.4 hereinafter, it is preferred that Nb2O5The value of/ZnO is 0.2 hereinafter, more preferable Nb2O5The value of/ZnO is below 0.1.
9. environmental protection optical glass described in any claim according to claim 1~3, which is characterized in that wherein: K2O/(Li2O +Na2O+K2O value) is 0.1~0.45, preferably K2O/(Li2O+Na2O+K2O value) is 0.12~0.4, more preferable K2O/(Li2O +Na2O+K2O value) is 0.15~0.35.
10. environmental protection optical glass described in any claim according to claim 1~3, which is characterized in that wherein: (Na2O+ K2O)/BaO is 0.2~2.0, preferably (Na2O+K2O)/BaO is 0.3~1.5, more preferable (Na2O+K2O)/BaO is 0.4~1.0.
11. environmental protection optical glass described in any claim according to claim 1~3, which is characterized in that wherein: (SiO2+ ZrO2)/(ZnO+TiO2) it is 0.55~3.0, preferably (SiO2+ZrO2)/(ZnO+TiO2) in 0.7~2.5, more preferably (SiO2+ ZrO2)/(ZnO+TiO2) it is 0.8~1.8.
12. environmental protection optical glass described in any claim according to claim 1~3, which is characterized in that wherein: BaO/ It (MgO+CaO+SrO+BaO) is 0.7~1.0, preferably BaO/ (MgO+CaO+SrO+BaO) is 0.8~1.0, more preferable BaO/ It (MgO+CaO+SrO+BaO) is 0.9~1.0.
13. environmental protection optical glass described in any claim according to claim 1~3, which is characterized in that wherein: (Li2O+ ZnO)/SiO2It is 0.35~1.2, preferably (Li2O+ZnO)/SiO2It is 0.4~1.0, more preferable (Li2O+ZnO)/SiO2It is 0.45 ~0.85.
14. environmental protection optical glass described in any claim according to claim 1~3, which is characterized in that the environmental protection optics The refractive index nd of glass is 1.64~1.71, preferably 1.65~1.70, more preferably 1.66~1.69；Abbe number νdFor 35~ 40, preferably 36~40, more preferably 36~39.
15. environmental protection optical glass described in any claim according to claim 1~3, which is characterized in that the environmental protection optics The water-fast effect stability D of glassWMore than 2 classes, preferably 1 class；And/or acidproof effect stability DAMore than 2 classes, preferably For 1 class.
16. environmental protection optical glass described in any claim according to claim 1~3, which is characterized in that the environmental protection optics The bubble degree of glass is B grades or more, preferably A grades or more, more preferably A0Grade or more；And/or striped degree is C grades or more, it is excellent Select B grades or more.
17. environmental protection optical glass described in any claim according to claim 1~3, which is characterized in that the environmental protection optics The thermalexpansioncoefficientα of glass20~120 DEG CIt is 85 × 10-7/ K is hereinafter, preferably 80 × 10-7/ K is hereinafter, more preferably 78 × 10-7/K Below；And/or crystallization ceiling temperature be 1150 DEG C hereinafter, preferably 1100 DEG C hereinafter, more preferably 1050 DEG C or less；And/or Transition temperature TgFor 600 DEG C hereinafter, preferably 590 DEG C hereinafter, more preferably 585 DEG C or less.
18. optical precast product is made of environmental protection optical glass described in claim 1~17 any claim.
19. optical element is made of environmental protection optical glass described in claim 1~17 any claim, or using power Benefit require 18 described in optical precast product be made.
20. optical instrument is wanted containing environmental protection optical glass described in claim 1~17 any claim, or containing having the right Optical element described in asking 19.
CN201910012401.1A 2019-01-07 2019-01-07 Environment-friendly optical glass, optical prefabricated member, optical element and optical instrument Active CN109626814B (en)

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